Multisyringe Flow Injection Analysis Research Articles

An overview of automated flow systems for total and isotopic analysis of strontium and yttrium in samples of environmental interest

Due to the different uses of radioactivity during the last decades, there has been an increase in the concentration of natural and artificial radionuclides in the environment. This, along with some accidents with a high affect public opinion (for example, Chernobyl and Fukushima), have led to the growth and establishment of environmental radioactivity monitoring programs. Currently, trends in legislation and research are focused on the development of accurate, precise, reliable and fast analytical methods with low limits of detection (LOD) for radionuclides determination, such as strontium and yttrium, in environmental samples. In this paper, two comprehensive reviews and four automated analytical systems for total and isotopic determination of yttrium and strontium are presented. The developed methods have been applied in the analysis of environmental samples with low concentrations of these analytes. These methodologies have been automated by exploiting flow analysis techniques, such as multi-syringe flow injection analysis (MSFIA), Sequential injection analysis (SIA) and laboratory-on-valve (LOV) systems, achieving a minimal handling and low consumption of samples and reagents, a significant reduction in waste generation and a high frequency of analysis. In the developed methodologies, some spectrometric methods such as ICP-OES and ICP-MS have been implemented as detection techniques instead of radiometric detectors obtaining a fully automated, low-cost and fast yttrium and strontium determinations.

Automated method for the solid phase extraction of tetracyclines in wastewater followed by fluorimetric determination

This work presents a multisyringe flow injection analysis (MSFIA) system for the automatic extraction and determination of tetracyclines in wastewater samples. The sample was adjusted with Na2EDTA buffer before solid-phase extraction with an Oasis HLB column used for the analyte preconcentration. The europium (Eu3+)-based and citrate-mediated method (using Tris-HCl buffer) was selected for the fluorimetric analysis (λexc/em = 400/612 nm). For fluorescence detection, a low-cost system consisting of an USB 2000 CCD detector and a 3D-printed support that holds a LED light source was used. Under optimized conditions, the proposed method provided low limits of detection (9.4 μg L−1) and quantification (31 μg L−1), and good values for intra-day (<4 %) and inter-day precisions (<6 %). Recoveries of spiked TCs in wastewater samples ranged from 87 to 106 %. The results of this work were in good agreement with the measurements obtained by liquid chromatography coupled to a fluorescence detector.

Simple and Fast Two-Step Fully Automated Methodology for the Online Speciation of Inorganic Antimony Coupled to ICP-MS

A very simple, fast and non-chromatographic methodology for inorganic antimony speciation based on Multisyringe Flow Injection Analysis (MSFIA) employing online hydride generation (HG) ICP-MS was developed. The fully automated analysis is performed in two steps: firstly, Sb(III) is quantified by ICP-MS after chemical vapor generation; then, total antimony is determined in the presence of potassium iodide as a pre-reducer of Sb(V) to Sb(III). The Sb(V) concentration is quantified by the difference between the total antimony and Sb(III) concentrations, reaching an analysis frequency of 30 h−1. The optimization was performed using a Box Behnken design. The MSFIA-HG-ICP-MS system allows the antimony speciation analysis with a detection limit of 0.016 µg L−1 for Sb(III), working in a linear range of 0.053 to 5.0 µg L−1. This method was applied for the determination of Sb(III) and Sb(V) in water samples from Maiorca Island, Spain, and the concentrations found varied from 0.10 to 0.14 µg L−1 for Sb(III) and from 0.12 to 0.28 µg L−1 for Sb(V). The results were validated by addition/recovery tests, obtaining recoveries between 90 and 111% in both cases. Furthermore, a good precision was achieved, 1.4% RSD, and sample and reagent consumption were reduced to a few mL, with the consequent decrease in waste generation. Thus, the proposed method is a good tool for the speciation of inorganic antimony at ultra-trace levels in waters, allowing its risk assessment.

Multisyringe Flow Injection Analysis of Tropomyosin Allergens in Shellfish Samples.

This paper presents the development and the application of a multisyringe flow injection analysis system for the fluorimetric determination of the major heat-stable known allergen in shrimp, rPen a 1 (tropomyosin). This muscle protein, made up of 284 amino acids, is the main allergen in crustaceans and can be hydrolyzed by microwave in hydrochloric acid medium to produce glutamic acid, the major amino acid in the protein. Glutamic acid can then be quantified specifically by thermal conversion into pyroglutamic acid followed by chemical derivatization of the pyroglutamic acid formed by an analytical protocol based on an OPA-NAC reagent. Pyroglutamic acid can thus be quantified between 1 and 100 µM in less than 15 min with a detection limit of 1.3 µM. The method has been validated by measurements on real samples demonstrating that the response increases with the increase in the tropomyosin content or with the increase in the mass of the shrimp sample.

Selenium inorganic speciation in beers using MSFIA-HG-AFS system after multivariate optimization

In this work, the use of a multisyringe flow injection analysis coupled to hydride generation atomic fluorescence spectrometry (MSFIA-HG-AFS) for inorganic selenium chemical speciation was proposed. A Doehlert design was applied to optimize the experimental conditions for hydride generation (NaBH4 and HCl concentrations). The limits of quantification (LoQ) obtained were 0.07 µg L−1, for total inorganic Se, and 0.08 µg L−1, for Se(IV). Accuracy and precision of the proposed analytical method were evaluated through analysis of standard reference material and addition and recovery tests. The optimized method was applied to analyses of eight samples of beer, produced in Spain, obtaining concentrations for Se(IV) (<0.08 – 0.46 ± 0.01 µg L−1), total inorganic Se (0.47 ± 0.01 – 3.04 ± 0.62 µg L−1) and Se(VI) (0.06 ± 0.01 – 3.00 ± 0.59 µg L−1). The proposed analytical method was accurate, precise and sensitivity for determination of selenium species in beer samples.

Automated separation and measurement of 226Ra and trace metals in freshwater, seawater and fracking water by online ion exchange chromatography coupled with ICP-MS

An online solid-phase extraction method combined with ICP-MS was developed to separate and quantify low levels of 226Ra and other metals in drinking water, lake, river and sea water, and fracking fluids. A dual-column lab-on-valve and multi-syringe flow injection analysis (LOV-MSFIA) system was developed to provide precise measurement of 226Ra in samples with total dissolved solids (TDS) less than 2%. For samples with higher levels of TDS (up to 20%), a triple-column LOV-MSFIA system was developed, which used AG 50 W-X8 cation exchange, Sr spec andNobias Chelate resins. Compared to earlier automated systems for Ra analysis, the dual and triple column systems described here were optimized to accommodate smaller sample volumes, more precise flow control and lower limits of detection (LOD). The LOV-MSFIA system coupled with ICP-MS is a significant improvement over traditional methods for low level 226Ra measurements, which require extended sample holding and/or analysis time. External calibration and standard addition were used to quantify the concentration of Ra for the LOV-MSFIA system. After method optimization, LODs for 226Ra as low as 4.3 mBq L−1 (1.75 fg L−1) were obtained in different sample matrices. The concentrations of selected metals were also measured on the triple-column system, together with Ra, with a total online processing time of 28.5 min per sample. Thus, the online LOV-MSFIA system is shown to be a powerful tool for the rapid analysis of low levels of 226Ra, as well as other metals, in various types of aqueous samples.

Design of an automatic spectrophotometric system

A Multi-Syringe Flow Injection Analysis (MSFIA) fluorometric system based on a 3D printing device hosting a CCD detector has been designed for the determination of quinine in soft drinks. A LED controlled by an electronic circuit was used as a radiation source. The entire system is connected to two USB outputs of a computer. The AutoAnalysis program has been used for data acquisition and treatment. The results are more accurate and precise than those obtained with a manual method using a conventional spectrofluorometer. This developed system is a viable alternative to reduce the consumption of reagents, the impact on the environment and reduce measurement costs.

Determination of total and bioavailable As and Sb in children's paints using the MSFIA system coupled to HG-AFS.

In this study, the use of hydride generation atomic fluorescence spectrometry (HG-AFS) coupled with the multi-syringe flow injection analysis (MSFIA) has been proposed in the application of the Doehlert design to optimise the determination of As and Sb in gouache and tempera children's paints. The determination of the total and bioavailable As and Sb in paint samples from various brands and colours was also investigated. The limits of quantification (LOQ) obtained for the determination of As and Sb were 14.0 and 8.6 ng g-1, respectively. The accuracy and precision of the method were evaluated through recovery tests (by the analyte addition method) at three levels for both elements, and by the analysis of certified reference materials of clay (CRM 052, Loamy Clay 1) and river water (SLRS-4). Twenty paint samples, manufactured in China, Italy, Spain and Brazil, were analysed. The concentrations of As varied between below LOQ (<14 ng g-1) and 136.0 ± 1.1 ng g-1 (average value of 101.0 ng g-1, n = 10), and Sb between below LOQ (<8.6 ng g-1) and 74.0 ± 5.4 ng g-1 (average value of 21.7 ng g-1, n = 17). The children's paint samples presented As and Sb concentrations that were below the maximum values established by the National Institute of Metrology, Quality and Technology (INMETRO), as well as by the European legislation Directive 2009/48/EC. Based on the obtained results for the total As and Sb concentrations, eight samples were selected to evaluate the migration or bioavailability of As and Sb after solubilisation in HCl solution. The obtained results showed that for the eight analysed samples, the concentration of both elements after solubilisation in HCl solution were below the LOQ (<16.2 ng g-1 for As and <7.1 ng g-1 for Sb). These values correspond to the limits of analytical concentrations of As and Sb established by INMETRO and the Brazilian Association of Technical Standards (ABNT). The determined concentrations of As and Sb guarantee the safety (with regards to these elements) for children when using the analysed paint samples since they do not cause any health risk. The analytical method for the determination of the total and bioavailable As and Sb in children's paints was efficient, accurate and precise.

Fully automatic system for lead monitoring in water

A fully automatic multisyringe flow injection analysis - lab on valve system (MSFIA-LOV) with assisted automatic stirring for Pb (II) determination exploiting a long path-length liquid waveguide capillary cell (LWCC) for spectrophotometric detection was developed. On-line extraction of lead was performed inside of a microcolumn using a selective solid phase extraction (PB-resin), followed by the Pb-PAR complex formation with 4-(2-pyridylazo) resorcinol (PAR) as chromogenic reagent, to obtain a spectrophotometric detection at 520 nm. The assistance of automatic mechanical agitation to increase the analytical signal was made by using a rotary motor whose movement through a stainless steel rod, allowed to form a submersible agitator device. The limit of detection (LOD) of the developed method is 0.79 μg L−1, allowing the analysis well below the guideline values for lead in drinking water. The analytical parameters achieved, such as the good precision (RSD 4.2%), the analysis frequency and its fully automation make of this method a portable tool for low-cost Pb (II) detection system for water samples. The method has been successfully validated by means of a groundwater certified reference material (BCR®-610). It was also applied to different water matrices (groundwater, commercial bottled water and tap water) with recoveries close to 100%.

Automated on-line liquid-liquid extraction in a multisyringe flow injection analysis manifold for migration studies in food-contact materials: analysis of 4,4´-dihydroxybiphenyl

ABSTRACTPackaging may represent a source of food contamination, as different organic compounds and degradation compounds may migrate from packaging to foodstuff. For fatty foods, rectified olive oil is the common simulant, which implies time-consuming and laborious liquid-liquid extraction (LLE) procedures to isolate the contaminant(s) from the oil. Here we propose a Multisyringe Flow Injection Analysis manifold to automate this sample treatment, using the monomer 4,4´-dihydroxybiphenyl as the contaminant. The LLE procedure, using water as extractant, was fully automated. After the on-line LLE, the resulting extract was pumped through a fluorescence detector, inside which a flow-cell filled with C18 silica gel solid support was placed. The analyte was pre-concentrated on the solid support (in which the analytical signal was directly recorded), so improving the sensitivity of the system. Under optimum conditions, the method detection limit is 0.05 mg kg−1, well within the specific migration limit of 6 mg kg−1. The method developed was compared with the standard CEN test method (off-line LLE and HPLC determination) observing savings in sample and reagents of 90% and a 7-fold increase in sample throughput.

Multisyringe flow injection analysis for the spectrophotometric determination of uranium (VI) with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol

The spectrophotometric determination of uranium (VI) has been developed using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (Br-PADAP). This reaction has been adapted to apply a multisyringe flow injection analysis (MSFIA) system with spectrophotometric detection. The ternary complex of uranium (VI)-(Br-PADAP)-F has been measured at 578 nm. The procedure was optimized using univariate method and two-level full factorial. Four variables (concentrations of Br-PADAP, CyDTA, NaF and sample volume) were regarded as factors in the extraction optimization. Results of the two-level full factorial design, showed that only two factors (concentration of Br-PADAP and CyDTA) are statistically significant. The calibration curve is linear over the range 0.3–5 mg L−1 uranium (VI) with a relative standard deviation of 4.0% (1 mg L−1 uranium (VI), n = 10). The recoveries of uranium in water samples were between 80 and 102%.

Advances in the Hyphenation of Flow Analysis Techniques with Liquid Separations for Pharmaceutical Analysis

This commentary critically discusses the main advances in the field of flow analysis techniques hyphenated with liquid separations for pharmaceutical analysis over the last 15 years. Flow analysis techniques provide a convenient way to perform chemical assays with significant benefits in terms of rapidity, simplicity and cost of instrumentation, economy, precision, versatility in sample handling and potential for automation. The first-generation flow injection analysis (FIA), developed in the 1970’s, has been supplemented by a host of second-generation and third-generation flow methods developed in the 1990’s and 2000’s such as sequential injection analysis (SIA) and multi-syringe flow injection analysis (MSFIA) [1]. However, the main drawback of these techniques is their limited ability to simultaneously determine several analytes. Therefore, the hyphenation of flow techniques with separation techniques is a very attractive because it enables multi-component analysis. It was the introduction of monolithic columns [2] that has made possible the direct coupling of flow techniques with liquid separations platforms and has led to the development of hyphenated approaches such as FIC, SIC and MSC [3-5]. In all these techniques, a separation column is inserted in the flow path between the point of sample introduction and the detector; the main principles of operation can be found in the relevant literature [3-7]. FIC, SIC and MSC offer distinct advantages in terms of rapidity, simplicity, versatility and capital costs compared with high performance liquid chromatography (HPLC) and have been applied to the determination of a large number of pharmaceuticals [3-5]. When simple mixtures are considered, these hyphenated methods produce results that are comparable to HPLC [8,9]. The main advances in the hyphenation of flow analysis techniques with liquid separations for the purposes of pharmaceutical analysis are identified below

Multisyringe flow injection analysis (MSFIA) for the automatic determination of total iron in wines.

This work presents a multisyringe flow injection analysis (MSFIA) system for the automatic spectrophotometric determination of total iron in wine. The reaction is based on the complexation of Fe(II) with 2-(5-bromo-2-pyridylazo)-5-(diethylamino)-phenol (Br-PADAP). Ascorbic acid was used as reducing reagent for Fe(III) to Fe(II) and, in this way, to determine the total iron content in wine. The absorbance of the Fe(II)-(Br-PADAP)2 complex was measured at 748 nm. The proposed method provided a working rage from 0.36 to 5 mg L-1 of Fe(II), with a detection limit of 0.11 mg L-1 of Fe(II), a relative standard deviation of 0.42% (3 mg L-1 of Fe(II), n = 10), and a 46 h-1 injection throughput. The system is very simple, rapid and selective, and has been successfully applied to determine total iron in red, rosé and white wine without any need for sample pre-treatment steps. The results agree well with ICP-AES, which used as a reference method.

3D printed device for the automated preconcentration and determination of chromium (VI)

A 3D printed device for the fully automated disk-based solid-phase extraction (SPE) of Cr (VI) from water samples has been fabricated. The compatibility of the use of organic solvents for analyte elution with 3D printed flow devices based on polymers fabricated using stereolithograph​y has been evaluated. The developed methodology comprises the complexation of Cr (VI) with 1, 5-diphenylcarbazide (DPC) in acidic medium and the subsequent retention of the complex in a SBD-RPS disk contained within the 3D printed device. A multisyringe flow injection analysis system with online spectrophotometric detection has been used for the automation of the method. The fabricated 3D printed device integrates the different components of the flow analysis manifold, including connectors and mixers, being a powerful approach towards the reproducible construction of highly integrated flow-based manifolds.The extracted Cr (VI)-DPC complex is eluted with a mixture of methanol- sulfuric acid and quantified at 540 nm. The effect on the analytical signal and the optimization of variables were evaluated using multivariate and univariate techniques. A detection limit of 1 ng Cr (VI) and a linear working range of 3.2–600 ng Cr (VI) were obtained using a sample volume of 2 ml. The intra-day and inter-day RSDs were 4.8% (10 µg L−1, n = 12) and 3.4% (n = 5, different day with a different disk), respectively. The applicability of the fabricated 3D printed device has been proved by the determination of Cr (VI) in groundwater, surface water and leachates.

3D printed device including disk-based solid-phase extraction for the automated speciation of iron using the multisyringe flow injection analysis technique

The development of advanced manufacturing techniques is crucial for the design of novel analytical tools with unprecedented features. Advanced manufacturing, also known as 3D printing, has been explored for the first time to fabricate modular devices with integrated features for disk-based automated solid-phase extraction (SPE). A modular device integrating analyte oxidation, disk-based SPE and analyte complexation has been fabricated using stereolithographic 3D printing. The 3D printed device is directly connected to flow-based analytical instrumentation, replacing typical flow networks based on discrete elements. As proof of concept, the 3D printed device was implemented in a multisyringe flow injection analysis (MSFIA) system, and applied to the fully automated speciation, SPE and spectrophotometric quantification of Fe in water samples. The obtained limit of detection for total Fe determination was 7ng, with a dynamic linear range from 22ng to 2400ng Fe (3mL sample). An intra-day RSD of 4% (n = 12) and an inter-day RSD of 4.3% (n = 5, 3mL sample, different day with a different disk), were obtained. Incorporation of integrated 3D printed devices with automated flow-based techniques showed improved sensitivity (85% increase on the measured peak height for the determination of total Fe) in comparison with analogous flow manifolds built from conventional tubing and connectors. Our work represents a step forward towards the improved reproducibility in the fabrication of manifolds for flow-based automated methods of analysis, which is especially relevant in the implementation of interlaboratory analysis.

Fully Automated System for 99Tc Monitoring in Hospital and Urban Residues: A Simple Approach to Waste Management.

99Tc is an artificial beta emitter widely used in nuclear medicine for diagnostic tests. A fully automated and rapid system for 99Tc monitoring is introduced with the aim to improve hospital residues management. This system can also be helpful for controlling urban wastewater. Figures of merit similar to those obtained with liquid scintillation counting were achieved by exploiting a simple, economic, and portable system with spectrophotometric detection. The combination of flow analysis techniques, i.e., lab-on-valve (LOV) and multisyringe flow injection analysis (MSFIA), with a selective resin ((weak base extraction chromatographic (WBEC) resin) enables the analysis to be performed in a short time, achieving high selectivity and sensitivity levels. After elution with NH4OH (3 mol·L-1), 99Tc is derivatized with 1,5-diphenylcarbohydrazide (DPC) and finally detected by a miniaturized fiber optic CCD spectrophotometer at 520 nm, exploiting a long path-length liquid waveguide capillary cell (LWCC) of 100 cm path length. The proposed method was optimized by experimental design, achieving a limit of detection (LOD) of 4 ng of 99Tc (2.5 Bq), a reproducibility of 6%, and a resin durability of 78 injections. The microcolumn allows one to preconcentrate up to 100 mL of sample without deterioration of the analytical signal. The automated system was successfully applied to hospital residues and urban wastewater, and the attained recoveries were between 90% and 110%.

Determination of phthalates in bottled water by automated on-line solid phase extraction coupled to liquid chromatography with uv detection

An on-line solid phase extraction coupled to liquid chromatography with UV detection (SPE/LC-UV) method was automated by the multisyringe flow-injection analysis (MSFIA) system for the determination of three phthalic acid esters (PAEs). The PAEs determined in drinking water stored in polyethylene terephthalate (PET) bottles of ten commercial brands were dimethyl phthalate (DMP), diethyl phthalate (DEP) and dibutyl phthalate (DBP). C18-bonded silica membrane was used for isolation and enrichment of the PAEs in water samples. The calibration range of the SPE/LC-UV method was 2.5–100μgL−1 for DMP and DEP and 10–100μgL−1 for DBP with correlation coefficients (r) ranging from 0.9970 to 0.9975. Limits of detection (LODs) were between 0.7 and 2.4μgL−1. Inter-day reproducibility performed at two concentration levels (10 and 100μgL−1) expressed as relative standard deviation (%RSD) were found in the range of 0.9–4.0%. The solvent volume was reduced to 18mL with a total analysis time of 48min per sample. The major species detected in bottled water samples was DBP reaching concentrations between 20.5 and 82.8μgL−1. The recovery percentages for the three analytes in drinking water were 80–115%. The migration test showed a great variation in the sum of migrated PAEs level (10.2–50.6μgL−1) among the PET bottle brands analyzed indicating that the presence of these contaminants in the plastic containers may depend on raw materials and the conditions used during their production process.

Automatic solid phase extraction of cadmium exploiting a multicommutated flow system previous ICP-MS detection: Application to tobacco samples

A miniaturized automatic sample pre-treatment system, based on multicommutated flow techniques, i.e. Lab on Valve (LOV) and Multisyringe Flow Injection Analysis (MSFIA) techniques, for cadmium determination by ICP-MS in organic samples is presented. The on-line extraction and preconcentration system retains the analyte on the resin (Dowex 50W-X8), followed of elution with 1molL−1 HNO3. The LOV-MSFIA system allows the fully automation of solid phase renewal, which shown a durability of 130 injections without its replacement. The optimal operating conditions were investigated using multivariate optimization tools. The detection limit was 0.05ng of cadmium, while the mass linear working range was 0.2–100ng. The precision of the proposed methodology was 2.4% (RSD, n=10) with a sample frequency of 9 injections h−1.The accuracy of the method was established by means of an organic matrix certified reference material (DORM-2), and the method has been successfully applied to different samples of tobacco (commercial cigarettes, pipe tobacco and tobacco leaves), obtaining recoveries between 90 and 105%. Main advantages of the proposed methodology are a minimal sample handling, good precision, high stability of the column and the versatility achieved by a variety of managed sample volumes.

On line automated system for the determination of Sb(V), Sb(III), thrimethyl antimony(v) and total antimony in soil employing multisyringe flow injection analysis coupled to HG-AFS

This paper proposes the use of a multisyringe flow injection analysis (MSFIA) system for inorganic antimony speciation analysis, trimethyl antimony(V) and determination of total antimony in soil samples using hydride generation atomic fluorescence spectrometry (HG-AFS). Total antimony has been determined after reduction of antimony(V) to antimony(III) using potassium iodide and ascorbic acid. For determination of total inorganic antimony the sample is percolated in a mini-column containing the Dowex 50W-X8 resin for retention of the organic species of antimony. Antimony(III) is quantified in presence of 8-hydroxyquinoline as masking agent for antimony(V) after an extraction step of the organic antimony species using the also same mini-column. The trimethyl antimony(V) content is found by difference between total antimony and total inorganic antimony. By other hand, antimony(V) is quantified by difference between total inorganic antimony and antimony(III). The analytical determinations were performed using sodium tetrahydroborate as reducing agent. The optimization step was performed using two-level full factorial design and Doehlert matrix involving the factors: hydrochloric acid and sodium tetrahydroborate concentrations and sample flow rate. The optimized experimental conditions allow the antimony determination utilizing the external calibration technique with limits of detection and quantification of 0.9 and 3.1ngg−1, respectively, and a precision expressed as relative standard deviation of 3.2% for an antimony solution of 5.0µgL−1. The method accuracy was confirmed by analysis of the soil certified reference material furnished from Sigma-Aldrich RTC. Additionally, addition/recovery tests were performed employing synthetic solutions prepared using trimethyl antimony(V), antimony(III), antimony(V) and five soil samples. The antimony extraction step was performed in a closed system using hydrochloric acid, ultrasonic radiation and controlled temperature. The method proposed was applied for analysis of thirteen soil samples collected in different sites of the Balearic Islands, Spain, and the results obtained varied from 19 to 46ngg−1 for trimethyl antimony(V) and from 113 to 215ngg−1 for total inorganic antimony. The concentrations obtained to antimony(V) were always higher than for antimony(III) in all the analyzed samples.

Multivariate optimisation of a rapid and simple automated method for bismuth determination in well water samples exploiting long path length spectrophotometry

ABSTRACTAn automated spectrophotometric system is proposed for the determination of bismuth in well water samples, using multi-syringe flow injection analysis (MSFIA) and exploiting a liquid waveguide capillary cell (LWCC). This method is based on the colorimetric reaction of bismuth and methylthymol blue (MTB) in the presence of polyvinylpyrrolidone (PVP) in acid medium (0.1 mol L−1 HNO3). The Bi(III)–MTB complex was measured at 600 nm. The method was optimised by multivariate techniques. Some figures of merit of the proposed system are worth being highlighted, such as its wide linear working range (between 4.9 and 600 μg L−1), its low detection limit (1.5 μg L−1 of bismuth) and its high intra-day precision and inter-day precision (0.7% (n = 12) and 1.4% (n = 5), respectively, both expressed as RSD). Moreover, a high injection frequency of 30 h−1 is achieved, as the proposed analyser is a powerful tool for fast Bi(III) determination. The method developed was successfully validated by analysing reference samples (pharmaceutical samples) by comparing the results with those obtained by ICP-OES and it was satisfactorily applied to well water samples. Besides, the present system is miniaturised allowing in situ measurements in control processes and field analysis.