An improved method for measuring soil microbial activity by gas phase flow injection analysis

The rate of carbon dioxide production is commonly used as a measure of microbial activity in the soil. The traditional method of CO2 determination involves trapping CO2 in an alkali solution and then determining CO2 concentration indirectly by titration of the remaining alkali in the solution. This method is still commonly employed in laboratories throughout the world due to its relative simplicity and the fact that it does not require expensive, specific equipment. However, there are several drawbacks: the method is time-consuming, requires large amounts of chemicals and the consistency of results depends on the operator's skills. With this in mind, an improved method was developed to analyze CO2 captured in alkali traps, which is cheap and relatively simple, with a substantially shorter sample handling time and reproducibility equivalent to the traditional titration method. A comparison of the concentration values determined by gas phase flow injection analysis (GPFIA) and titration showed no significant difference (p > 0.05), but GPFIA has the advantage that only a tenth of the sample volume of the titration method is required. The GPFIA system does not require the purchase of new, costly equipment but the device was constructed from items commonly found in laboratories, with suggestions for alternative configurations for other detection units. Furthermore, GPFIA for CO2 analysis can be equally applied to samples obtained from either the headspace of microcosms or from a sampling chamber that allows CO2 to be released from alkali trapping solutions. The optimised GPFIA method was applied to analyse CO2 released from degrading hydrocarbons from a site contaminated by diesel spillage.

Automated flow-injection method for cadmium determination with pre-concentration and reagent preparation on-line

The spectrophotometric determination of Cd(II) using a flow injection system provided with a solid-phase reactor for cadmium preconcentration and on-line reagent preparation, is described. It is based on the formation of a dithizone-Cd complex in basic medium. The calibration curve is linear between 6 and 300 µg L-1 Cd(II), with a detection limit of 5.4 µg L-1, an RSD of 3.7% (10 replicates in duplicate) and a sample frequency of 11.4 h-1. The proposed method was satisfactorily applied to the determination of Cd(II) in surface, well and drinking waters.

Flow injection green method for the quantitative analysis of ketoconazole in pharmaceutical preparations

A flow injection method for the quantitative analysis of ketoconazole in tablets, based on the reaction with iron (III) ions, is presented. Ketoconazole forms a red complex with iron ions in an acid medium, with maximum absorbance at 495 nm. The detection limit was estimated to be 1×10--4 mol L-1; the quantitation limit is about 3×10--4 mol L-1 and approximately 30 determinations can be performed in an hour. The results were compared with those obtained with a reference HPLC method. Statistical comparisons were done using the Student's t procedure and the F test. Complete agreement was found at the 0.95 significance level between the proposed flow injection and the HPLC procedures. The two methods present similar precision, i.e., for HPLC the mean relative standard deviation was ca. 1.2% and for FIA ca. 1.6%.

Determination of cinnamic acid in human urine by flow injection chemiluminescence

It was found that cinnamic acid can react with potassium permanganate in the acidic medium and produce chemiluminescence, which was greatly enhanced by glyoxal. Under the optimum conditions, the linear range for the determination of cinnamic acid was 1.0×10-8 to 1.0×10-4 mol L-1 with a detection limit of 8.0×10-9 mol L-1, the relative standard deviation was 1.7% for 2.0×10-6 mol L-1 cinnamic acid solution in nine repeated measurements. This method was found to be novel0simple0fast and sensitive, it was successfully applied to the determination of cinnamic acid in human urine. Furthermore, the possible reaction mechanism was also discussed.

Determination of sulfate in the wet-process of phosphoric acid by reverse flow injection

An improved method based on reverse flow injection is proposed for determining sulfate concentration in the wet-process of phosphoric acid (WPA). The effect of reagent composition, flow rate, temperature, acid concentration, length of the reaction coil, and linear response range on the flow system is discussed in detail. Optimal conditions are established for determining sulfate in the WPA samples. Baseline drift is avoided by a periodic washing step with EDTA in an alkaline medium. A linear response is observed within a range of 20 - 360 mg L-1, given by the equation A = 0.0020C (mg L-1) + 0.0300, R² = 0.9991. The detection limit of the proposed method for sulfate analysis is 3 mg L-1, and the relative standard deviation (n = 12) of sulfate absorbance peak is less than 1.60%. This method has a rate of up to 29 samples per hour, and the results compare well with those obtained with gravimetric method.

Direct determination of calcium in milk by atomic absorption spectrometry using flow-injection analysis

A flow-injection system with sample and reagent addition by the synchronous merging zones approach for calcium determination in milk by flame AAS is proposed. Main parameters were optimized using a factorial design with central point. The optimum conditions were 2.5% (m/v) for La concentration, 8 mL min-1 for the carrier flow-rate, 20 cm for coiled reactor and 250 ìL for sample volume. Different sample preparation procedures were evaluated such as dilution in water or acid and microwave-assisted decomposition using concentrated or diluted acids. The optimized flow system was applied to determine Ca in eleven commercial milk samples and two standard reference materials diluted in water. Similar calcium levels were encountered comparing the results obtained by the proposed method (dilution in water) with those obtained using microwave-oven digestion. Results obtained in two standard reference materials were in agreement at 95% confidence level with those certified. Recoveries of spiked samples were in the 93% - 116% range. Relative standard deviation (n = 12) was < 5.4% and the sample throughput was 150 measurements per hour, corresponding to a consumption of 250 µL of sample and 6.25 mg La per determination.

Flow injection visible diffuse reflectance quantitative analysis of total sulfur in biodiesel, in plant leaves and in natural waters

Flow injection (FI) methodology, using diffuse reflectance in the visible region of the spectrum, for the analysis of total sulfur in the form of sulfate, precipitated in the form of barium sulfate, is presented. The method was applied to biodiesel, to plant leaves and to natural waters analysis. The analytical signal (S) correlates linearly with sulfate concentration (C) between 20 and 120 ppm, through the equation S=-1.138+0.0934 C (r = 0.9993). The experimentally observed limit of detection is about 10 ppm. The mean R.S.D. is about 3.0 %. Real samples containing sulfate were analyzed and the results obtained by the FI and by the reference batch turbidimetric method using the statistical Student's t-test and F-test were compared.

A pH optode based on thymol blue: application to determination of CO2 using flow injection analysis system

An optode based on thymol blue (TB), an acid-based indicator, has been constructed and evaluated as a detector in FIA system for CO2 determination. The dye was chemically immobilised on the surface of a bifurcated glass optical fibre bundle, using silanisation in organic media. In FIA system, hydrogen carbonate or carbonate samples are injected in a buffer carrier solution, and then are mixed with phosphoric acid solution to generate CO2, which diffuses through a PTFE membrane, in order to be collected in an acceptor carrier fluid, pumped towards to detection cell, in which the optode was adapted. The proposed system presents two linear response ranges, from 1.0 x 10-3 to 1.0 x 10-2 mol l-1, and from 2.0 x 10-2 to 0.10 mol l-1. The sampling frequency was 11 sample h-1, with good repeatability (R.S.D < 4 %, n = 10). In flow conditions the optode lifetime was 170 h. The system was applied in the analysis of commercial mineral water and the results obtained in the hydrogen carbonate determination did not differ significantly from those obtained by potentiometry, at a confidence level of 95 %.

Flow injection analysis (FIA) determination of lead by hydride generation in banded coral skeletons /

A flow injection hydride generation direct current plasma atomic emission spectrometric (FI-HG-DCP-AES) method was developed for the determination of lead at ng.ml-l level. Potassium ferricyanide (K3Fe(CN)6) was used along with sodium tetrahydroborate(III) (NaBH4) to produce plumbane (PbH4) in an acid medium. The design of a gas-liquid separator (hydride generator) was tested and the parameters of the flow injection system were optimized to achieve a good detection limit and sample throughput. The technique developed gave a detection limit of 0.7 ng.ml-l(3ob). The precision at 20 ng.ml"* level was 1.6 % RSD with 1 1 measurements (n=l 1). Volume of sample loop was 500 |J.l. A sample throughput of 120 h"^ was achieved. The transition elements, Fe(II), FeOH), Cd(n), Co(II), Mn(n), Ni(II) and Zn(n) do not interfere in this method but 1 mg,l'l Cu(II) will suppress 50 % of the signal from a sample containing 20 ng.ml'l Pb. This method was successfully applied to determine lead in a calcium carbonate (CaC03) matrix of banded coral skeletons from Si-Chang Island in Thailand.

Investigations in flow injection analysis (FIA): conventional FIA determination of chloride in water; sequential injection (SI)-FIA determination of mercury in water

Flow injection analysis (FIA) was applied to the determination of both chloride ion and mercury in water. Conventional FIA was employed for the chloride study. Investigations of the Fe3 +/Hg(SCN)2/CI-,450 nm spectrophotometric system for chloride determination led to the discovery of an absorbance in the 250-260 nm region when Hg(SCN)2 and CI- are combined in solution, in the absence of iron(III). Employing an in-house FIA system, absorbance observed at 254 nm exhibited a linear relation from essentially 0 - 2000 Jlg ml- 1 injected chloride. This linear range spanning three orders of magnitude is superior to the Fe3+/Hg(SCN)2/CI- system currently employed by laboratories worldwide. The detection limit obtainable with the proposed method was determin~d to be 0.16 Jlg ml- 1 and the relative standard deviation was determined to be 3.5 % over the concentration range of 0-200 Jig ml- 1. Other halogen ions were found to interfere with chloride determination at 254 nm whereas cations did not interfere. This system was successfully applied to the determination of chloride ion in laboratory water. Sequential injection (SI)-FIA was employed for mercury determination in water with the PSA Galahad mercury amalgamation, and Merlin mercury fluorescence detection systems. Initial mercury in air determinations involved injections of mercury saturated air directly into the Galahad whereas mercury in water determinations involved solution delivery via peristaltic pump to a gas/liquid separator, after reduction by stannous chloride. A series of changes were made to the internal hardware and valving systems of the Galahad mercury preconcentrator. Sequential injection solution delivery replaced the continuous peristaltic pump system and computer control was implemented to control and integrate all aspects of solution delivery, sample preconcentration and signal processing. Detection limits currently obtainable with this system are 0.1 ng ml-1 HgO.

Nickel hydroxide electrodes as amperometric detectors for carbohydrates in flow injection analysis and liquid chromatography

The present paper describes the utilization of nickel hydroxide modified electrodes toward the catalytic oxidation of carbohydrates (glucose, fructose, lactose and sucrose) and their utilization as electrochemical sensor. The modified electrodes were employed as a detector in flow injection analysis for individual carbohydrate detection, and to an ionic column chromatography system for multi-analyte samples aiming a prior separation step. Kinetic studies were performed on a rotating disk electrode (RDE) in order to determine both the heterogeneous rate constant and number of electrons transferred for each carbohydrate. Many advantages were found for the proposed system including fast and easy handling of the electrode modification, low cost procedure, a wide range of linearity (0.5-50 ppm), low detection limits (ppb level) and high sensitivities. (C) 2009 Elsevier B.V. All rights reserved.

Flow injection amperometric determination of hydrogen peroxide in household commercial products with a ruthenium oxide hexacyanoferrate modified electrode

Hydrogen peroxide was determined in oral antiseptic and bleach samples using a flow-injection system with amperometric detection. A glassy carbon electrode modified by electrochemical deposition of ruthenium oxide hexacyanoferrate was used as working electrode and a homemade Ag/AgCl (saturated KCl) electrode and a platinum wire were used as reference and counter electrodes, respectively. The electrocatalytic reduction process allowed the determination of hydrogen peroxide at 0.0 V. A linear relationship between the cathodic peak current and concentration of hydrogen peroxide was obtained in the range 10-5000 mu mol L(-1) with detection and quantification limits of 1.7 (S/N = 3) and 5.9 (S/N = 10) mu mol L(-1), respectively. The repeatability of the method was evaluated using a 500 mu mol L(-1) hydrogen peroxide solution, the value obtained being 1.6% (n = 14). A sampling rate of 112 samples h(-1) was achieved at optimised conditions. The method was employed for the quantification of hydrogen peroxide in two commercial samples and the results were in agreement with those obtained by using a recommended procedure.

Flow injection analysis using carbon film resistor electrodes for amperometric determination of ambroxol

Flow injection analysis (FIA) using a carbon film sensor for amperometric detection was explored for ambroxol analysis in pharmaceutical formulations. The specially designed flow cell designed in the lab generated sharp and reproducible current peaks, with a wide linear dynamic range from 5 x 10(-7) to 3.5 x 10(-4) mol L-1, in 0.1 mol L-1 sulfuric acid electrolyte, as well as high sensitivity, 0.110 A mol(-1) L cm(-2) at the optimized flow rate. A detection limit of 7.6 x 10(-8) mol L-1 and a sampling frequency of 50 determinations per hour were achieved, employing injected volumes of 100 mu L and a flow rate of 2.0 mL min(-1). The repeatability, expressed as R.S.D. for successive and alternated injections of 6.0 x 10(-6) and 6.0 x 10(-5) mol L-1 ambroxol solutions, was 3.0 and 1.5%, respectively, without any noticeable memory effect between injections. The proposed method was applied to the analysis of ambroxol in pharmaceutical samples and the results obtained were compared with UV spectrophotometric and acid-base titrimetric methods. Good agreement between the results utilizing the three methods and the labeled values was achieved, corroborating the good performance of the proposed electrochemical methodology for ambroxol analysis. (C) 2008 Elsevier B.V. All rights reserved.

Flow-injection spectrophotometric determination of dipyrone in pharmaceutical formulations using ammonium molybdate as chromogenic reagent

A simple and rapid flow-injection spectrophotometric method is reported for the determination of dipyrone in pharmaceutical formulations. The method is based on the reaction of dipyrone with ammonium molybdate in acidic medium to produce blue molybdenum, which was detected spectrophotometrically at 620 nm. The analyte was determined in a single-line flow system. The calibration curve obtained was linear in the range of 5x10(-4) to 8x10(-3) mol L-1 for dipyrone concentration and the precision ( s r =1.7%) was satisfactory. The method proved to be selective and adequately sensitive. Application of the method to the analysis of pharmaceutical samples resulted in excellent accuracy; the percent mean recoveries were in the range 95.3%-101% and relative errors less than 5.0% for five pharmaceutical formulations were found.

An electrochemical sensor for (L)-dopa based on oxovanadium-salen thin film electrode applied flow injection system

An oxovanadium-salen complex (NAP-ethylene-bis(salicylidenciminato) oxovanadium) thin film deposited on a graphite-polyurethane electrode was investigated with regard to its potential use for detection of L-dopa in flow injection system. The oxovanadium(IV)/oxovanadium(V) redox couple of the modified electrode was found to mediate the L-dopa oxidation before its use in the FIA system. Experimental parameters, such as pH of the carrier solution, flow rate, sample volume injection and probable interferents were investigated. Under the optimized FIA conditions, the amperometric signal was linearly dependent on the L-dopa concentration over the range 1.0 x 10(-1) to 1.0 x 10(-4) mol L-1 (I-anodic, mu A) = 0.01 + 0.25 [L-dopa mu mol L-1]) with a detection limit (S/N = 3) of 8.0 x 10(-7) mol L-1 and a sampling frequency of 90 h(-1) was achieved. For a concentration of 1.0 x 10(-5) mol L-1 L-dopa, the R.S.D. of nine consecutive measurements was 3.7%. (c) 2006 Elsevier B.V. All rights reserved.