Flow Injection Manifold Research Articles

Direct Determination of Iron(II) in Acid dified Seawater using a Matrix Matched Flow Injection Manifold with Chemilminescence Detection Original Paper

Direct Determination of Iron(II) in Acid dified Seawater using a Matrix Matched Flow Injection Manifold with Chemilminescence Detection Original Paper

Preparation of a soluble solid sample by a continuous ultrasound assisted dissolution system for the flow-injection atomic absorption spectrometric determination of iron in milk powder and infant formula

A simple and new flow-injection manifold (CUDS) for the continuous ultrasound assisted dissolution of a soluble solid sample coupled to a flow-injection flame atomic absorption spectrometric manifold for the continuous iron determination is described. An experimental design was used for the evaluation of factors involving the CUDS. The method was applied to a certified reference material (CRM-151, skim milk powder) for quality assurance/validation and to real samples (milk powder and infant formulas). The total sampling frequency achieved was 80 samples per hour with a relative standard deviation for the complete procedure of 1.1%. The detection limit was 0.60 μg g −1 for a sample amount of 30 mg. The results demonstrated that the CUDS is an innovative and efficient tool as compared to the manual–traditional sample preparation methods, but with drastic increase of both sample throughput and precision.

Continuous Ultrasound-Assisted Leaching of Phenoxyacid Herbicides in Soil and Sediment with in-situ Sample Treatment

Ultrasound, water and Na2EDTA·2H2O have been used for continuous leaching with in-situ sample treatment of acid herbicides (namely, bentazone, 2,4-D, trichlopyr, 2,4,5-T and 2,4,5-Tp) from different types of soil (namely, clayey, slimy, sandy, organic and limy) and one sediment. The subsequent steps for quantitation of the leached analytes (namely, preconcentration, individual chromatographic separation and UV detection) were performed using a flow injection manifold that permits automation of the overall process. The main factors contributing to the leaching efficiency—namely, ultrasound radiation amplitude, probe position, percentage of duty cycle of ultrasound exposure, extractant flow-rate and temperature of the water bath in which the extraction cell is immersed—were optimized by means of a central composite design. Also, the kinetics of the leaching step with Na2EDTA·2H2O was studied. In all cases, the recoveries of the target analytes were higher than 92%. The detection and quantification limits were 10 and 30 ng g−1, respectively, for all analytes, but trichlopyr (detection and quantification limits 5 and 12 ng g−1, respectively). The relative standard deviations for repeatability range between 2.8–5.3%.

Flow injection on-line ultrasound-assisted extraction of iron in meat samples coupled to a flame atomic absorption spectrometric system.

Iron was extracted on-line from solid meat samples by a simple and rapid continuous ultrasound-assisted extraction system (CUES). The CUES is connected to a flow injection manifold, which allows the on-line flame atomic absorption spectrometric determination of iron. A Plakett-Burman design was used for the optimisation of the CUES. The method achieved a total sampling frequency of 11 samples per hour with a relative standard deviation for the complete procedure of 0.4%. The detection limit was 0.6 microg g(-1) (dry mass) for a sample amount of 30 mg. Accurate results were obtained by measuring the certified reference materials BCR-186 (pig kidney) and BCR-184 (bovine muscle). The analytical procedure was applied to different real meat samples with satisfactory results.

Comparison of the static, dynamic and static-dynamic pressurised liquid extraction modes for the removal of nitrated polycyclic aromatic hydrocarbons from soil with on-line filtration-preconcentration

The three operational modes of pressurised liquid extraction (PLE) (namely, static, dynamic and static-dynamic) have been applied for the extraction of nitrated polycyclic aromatic hydrocarbons from both spiked and natural contaminated soils. A comparison of the three modes in terms of experimental set-up used, extraction time needed for total removal of the analytes and precision has been carried out. The use of a flow-injection manifold as interface between every pressurised extractor and a filtration-preconcentration system has allowed the partial automation of the proposed approaches. Efficiencies close to 100% have been provided by the three operational modes. However, the static-dynamic mode has been proved as the most suitable alternative providing the shortest extraction time (25 min) versus the static (30 min) and the dynamic (50–70 min) modes. Gas chromatography with MS–MS ion preparation mode has been used providing both high selectivity (no interferences were observed) and sensitivity (detection limits of low pg). The comparison of the proposed approaches with the reference method 3540 of the US Environmental Protection Agency (EPA) has shown that both methods provide similar efficiencies with an important shortening in the extraction time (25–70 min by PLE versus 24 h by the EPA method). The use of water as leaching agent has avoided the use of organic solvents providing an environmentally friendly method.

Flow injection manifolds for liquid–liquid extraction without phase separation assisted by ultrasound

Flow injection (FI) manifolds based on iterative change of the flow direction have been designed to study the influence of auxiliary energy on continuous liquid–liquid extraction without phase separation and compare it with the non-assisted process in a single experiment. In order to demonstrate the utility of ultrasounds as auxiliary energy for the extraction of polyphenols from an organic phase, the approach has been applied to samples of extra virgin olive oil, using an alkaline aqueous phase as extractant and subsequent derivatization with the Folin–Ciocalteu reagent. The proposed method provides results similar to those from the official method-recoveries between 97 and 100%. The sensitivity of the proposed method is 3.5 times higher than that of the non-ultrasound-assisted method. The precision, expressed as relative standard deviation (R.S.D.) for n=5, was within 1–5% and the relative errors for the irradiated and non-irradiated method were within 3 and 5%, respectively. The repeatability and within-laboratory reproducibility, studied at two concentration levels (379 and 813 μg ml −1) ranged between 0.7–4.4% and 0.6–4.8%, respectively. The proposed manifolds can also be applied to either other type of auxiliary energies—microwave, thermal—or two different types of auxiliary energies at the same time.

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.

Flow and Sequential Injection Manifolds for the Spectrophotometric Determination of Captopril Based on its Oxidation by Fe(III)

Two new simple and rapid methods are reported for the accurate and precise spectrophotometric determination of captopril (CPL) using flow (FI) and sequential injection (SI) analysis. The methods are based on the fast oxidation of CPL by Fe(III). The produced Fe(II) reacts with 2,2′-dipyridyl-2-pyridylhydrazone (DPPH) in acidic medium to form a colored complex which is monitored spectrophotometrically at 535 nm. Both methods allow the determination of the analyte up to 1000 mg L−1 at a sampling rate of 120 and 60 injections per hour for FI and SI, respectively. The methods are very precise [s r=0.8 and 1.2% at 500 mg L−1 CPL (n=12) for FI and SI, respectively] and the 3σ detection limits (c L=4.0 and 7.0 mg L1, respectively) are quite satisfactory. Their application to a variety of anti-hypertensive commercial pharmaceutical formulations showed excellent results (relative errors, e r, < ± 1.6% in all cases compared to an official HPLC method), while common pharmaceutical excipients were found not to interfere. Recovery experiments further verified the accuracy of the developed methods, as the percent recoveries were in the range of 98.1–102.5%.

Sequential flow injection determination of iodate and periodate with spectrophotometric detection

A flow injection (FI) system is described for the sequential determination of periodate and iodate based on their reaction with iodide at pH 3.5. Two sample plugs were injected into the same carrier stream sequentially. One injection is for the iodate determination and the other for the sum of iodate and periodate determination. For iodate determination, molybdate solution buffered at pH of 3.5 was used for selective masking of periodate. The influences of reagent concentrations were studied by a univariable method and the influence of FI manifolds was studied using univariable and simplex method. Periodate and iodate can be determined in the range of 0.050–5.0 and 0.050–10 μg/ml, respectively. The 3σ limit of detection was 0.030 and 0.050 μg/ml for periodate and iodate, respectively. The proposed method has been applied for the sequential determinations of periodate and iodate in water samples.

Continuous ultrasound-assisted extraction coupled to on line filtration–solid-phase extraction–column liquid chromatography–post column derivatisation–fluorescence detection for the determination of N-methylcarbamates in soil and food

A dynamic ultrasound-assisted method for the extraction of N-methylcarbamates (oxamyl, dioxacarb, metolcarb, carbofuran, carbaryl and isoprocarb) from soils and foods is proposed. The main factors affecting the extraction efficiency have been optimised by means of a central composite design. Pure water can be used as leaching agent. A flow injection manifold coupled to the extractor allows automation of the several steps involved in the analytical process. The method allows extraction of the carbamates from soil and food at 1 μg/g spiked level, with recoveries similar to those provided by the EPA 8318 method, without degradation of the target compounds during the extraction and with drastic shortening of the time required for this step (2 min vs. 4 h). Recoveries of the target analytes were 77–95% for spiked soil and 85–101% for spiked food. The detection and quantification limits were 12 and 40 ng/g, respectively, for all analytes, except carbaryl (detection and quantification limits 3 and 10 ng/ng, respectively). The relative standard deviations for repeatability and within-laboratory reproducibility were 3.1 and 7.5%, respectively.

Slurry Sampling-Microwave Assisted Leaching Prior to Hydride Generation-Pervaporation-Atomic Fluorescence Detection for the Determination of Extractable Arsenic in Soil

A flow injection-pervaporation method, where the sample was introduced as slurry, has been developed for the continuous derivatization and determination of arsenic in soil by hydride generation-atomic fluorescence spectrometry. The removal of arsenic is achieved with the help of a microwave digestor, which facilitates an on-line leaching in the flow injection manifold. Slurries, prepared by mixing the soil (particle size <65 microm) with 6 mol L(-)(1) HCl, were magnetically stirred for 3 min, and while stirring, the pump aspirated the aliquot and filled the loop (500 microL) of the injection valve. An industrial soil and five types of soil (sandy, clayey, slimy, limy, organic) were selected for the optimization of the leaching and determination steps of arsenic, respectively. The results obtained from three certified reference materials [stream sediment GBW 07311 (188 microg/mL As), river sediment CRM 320 (76.7 microg/mL As), and soil GBW 07405 (412 microg/mL As)] using direct calibration against aqueous standards demonstrate the reliability of the method. The relative standard deviation for within-laboratory reproducibility was 4.5%.

Reverse flow-injection manifold for spectrofluorimetric determination of aluminum in drinking water

A simple reverse flow-injection (rFIA) manifold for the direct determination of aluminum in drinking water is proposed. This rapid and sensitive method is based on the formation of an Al 3+ complex with salicylaldehyde picolinoylhydrazone (SAPH), which shows a maximum blue-green fluorescence ( λ ex=384 nm, λ em= 468 nm) at pH 5.4. Operative conditions both for batch and rFIA procedures were investigated including reagent concentration, buffer solutions, injection loop, reacting coil and wavelengths used for the fluorimetric detection. The tolerance limits of foreign ions have been also evaluated, before and after the addition of masking agents. The reverse flow-injection procedure allows determination of Al 3+ at ppb level (LOD: 1.9 μg l −1) within a working range of 5–30 μg l −1. The proposed method was successfully employed for the determination of Al 3+ in several commercial drinking, soft drinking (as certified reference material), and tap water samples.

Analytical Pervaporation: A Key Technique in the Enological Laboratory

This paper reviews the use of analytical pervaporation (defined as the integration of 2 different analytical separation principles, evaporation and gas diffusion, in a single micromodule) coupled to flow-injection manifolds for the determination of analytes of interest in enology; the review discusses the advantages that these techniques can provide in wine analytical laboratories. Special attention is given to methods that enable the determination of either of 2 volatile analytes, or of one volatile analyte and one nonvolatile analyte by taking advantage of the versatility of the designed approaches. In a comparison of these methods with the official and/or standard methods, the results showed good agreement. In addition, the new methods offer improvements in linear determination range, quantitation limit, precision, rapidity, and potential for full automation. Thus, this review demonstrates that although the old technologies used in wine analytical laboratories may be supported by official and standard methods, they should be replaced by properly validated, new, and automated technologies.

Valves and flow injection manifolds: an excellent marriage with unlimited versatility

An overview of the functions of valves—both injection and selection valves—in flow injection (FI) for manipulating the manifold as a function of both necessities and imagination of the user is reported. The use of single valves for sample or reagent injection, for housing different devices (namely, minicolumns and other separation units, flow-cells, etc.) is discussed. Multiple injection valve arrangements (in-series, in-parallel and inner coupling) that give place to FI modes as merging-zones (both symmetrical and asymmetrical), trapping-zone and nested-loop approaches are exposed. The possible locations of selection valves in the FI manifold are presented and the problems each design can solve are commented.

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.

Flow Injection Electrochemical Determination of Apomorphine

Few analytical methods are currently available for determination of apomorphine, the active substance of a new oral formulation used in the treatment of erectile dysfunction. In this way a flow injection electrochemical method (FIA-EC) was developed for its quantification and applied to pharmaceutical dosage forms. Based in previous findings regarding the stability of apomorphine in borate buffer and after optimization of several analytical parameters a single channel flow injection manifold was set up that enables the determination of this drug over the concentration range of 3 to 16 µmol L−1 with a detection limit of 0.5 µmol L−1 at a sampling rate of 90 h−1. The simplicity and rapidity of the FIA-EC method used, its reproducibility and sensitivity make it suitable for quality control of pharmaceutical preparations of apomorphine intended for clinical use and research.

Evaluation of non-chromatographic approaches for speciation of extractable As(III) and As(V) in environmental solid samples by FI-HGAAS

Non-chromatographic speciation approaches have been developed for determination of water-soluble and phosphate-exchangeable As(III) and As(V) in certified reference materials of coal fly ash and sediments by FI-HGAAS. A 2 IV 6–2 fractional factorial design was employed for screening optimisation of the flow injection manifold. A simple two-stage sequential extraction protocol involving deionized water and a phosphate buffer as extractants was employed. Determination of both oxidation states of As in the extracts could be accomplished following arsine generation under different reaction conditions, namely, (i) selective determination of As(III) in citric acid medium or using soft generation conditions (i.e. low HCl and NaBH 4 concentrations); (ii) determination of total As in each extract using thioglycollic acid as reaction medium or after pre-reduction of As(V) to As(III) with a KI+ascorbic acid mixture. The As(V) content was estimated by difference between both measurements. Reaction conditions were previously optimised and analytical parameters in each reaction medium were established. Overall, the extractable As content was less than 5% in sediment and fly ash CRMs. The LOD of As was around 0.07 μg l −1 for As(III) determination, and 0.06 μg l −1 for total As determination after prereduction. Liquid chromatography coupled to atomic fluorescence spectrometry with post-column hydride generation was used for comparison.

Mass distribution in a dynamic sample zone inside a flow injection manifold: modelling integrated conductimetric profiles

A mathematical model for fitting the experimental ICM (integrated conductimetric method) curves developed by the authors in a previous work, is presented for the first time in this study. The proposed model fits the experimental curves with great precision and allows to predict physical dispersion for single-line flow injection system. The correlation of the model’s parameters with typical reactionless FIA peak parameters is also assessed. The IDQ coefficient—a novel dispersion estimator previously reported by the authors—can also be predicted when operational FIA variables are changed. Experimental and modelled profiles are compared as a function of the system’s variables, showing an excellent agreement.

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%.

Static extraction with modified pressurized liquid and on-line fluorescence monitoring. Independent matrix approach for the removal of polycyclic aromatic hydrocarbons from environmental solid samples.

The coupling of a static pressurized liquid extractor to a flow injection manifold has allowed real-time on-line fluorescence monitoring of the polycyclic aromatic hydrocarbons (PAHs) extracted from environmental solid samples, which can be used for either screening or semiquantitative purposes. Sodium dodecyl sulfate (SDS) was added to the water for favoring the extraction of the low-polar analytes. Different solid samples such as sandy soil, river sediments, trout and sardine spiked with the target PAHs were subjected to several 15-min static extraction cycles with SDS-water, at 200 degrees C. The results obtained demonstrated that fluorometric monitoring of static pressurized liquid extraction constitutes an approach as efficient as conventional Soxhlet for the extraction of PAHs from solid samples but with the following positive features: (a) drastic reduction of the extraction time as the extraction kinetics can be monitored and thus the end of the leaching step determined independently of the sample matrix; (b) use of water as extractant thus given place to an environmentally friendly method; and (c) coupling of static extraction to subsequent dynamic steps. The method has been applied to a certified reference material (CRM 524, BCR, industrial soil/organics) for quality assurance/validation. The total content of each analyte was determined by HPLC-fluorimetric detection.