Determination of total phosphorus in waters with amperometric detection by coupling of flow-injection analysis with continuous microwave oven digestion

For the determination of total phosphorus in waters by flow-injection analysis, a continuous microwave oven decomposition with subsequent amperometric detection of orthophosphate is proposed. The percentage digestion was examined for two different decomposition reagents and by varying the pH of the carrier and the length and diameter of the digestion coil. With potassium peroxodisulphate decomposition the recoveries of phosphorus vary from 91 to 100% for organic phosphorus compounds, and with perchloric acid decomposition the recoveries vary from 60 to 70% for inorganic polyphosphates. Calibration graphs are linear for up to 30 mg P l^?1, the determination limit is 0.1 mg P l^?1 and the precision of the method is 3% (relative standard deviation) (n = 5) at 5 mg P l^?1. The sampling rate is 20 h^?1. Good recoveries of phosphorus after addition to domestic waste water sample are obtained.     

Determination of nitrite and nitrate in Venice lagoon water by ion interaction reversed-phase liquid chromatography

Ion interaction reversed-phase liquid chromatography with octylammonium orthophosphate as the interacting reagent and a reversed-phase C₁₈ column was applied to the identification and determination of nitrite and nitrate in Venice lagoon water. Interference by the high chloride concentration was systematically studied and the results obtained with different column packings were compared. With spectrophotometric detection at 230 nm, nitrite at 0.005 mg 1^?1 can be detected and determined even in the presence of 0.70 M chloride. The dependence of the retention time of nitrite on the chloride concentration was studied for two reversed-phase columns with different packings. Concentrations of 0.30 ± 0.05 mg 1^?1 of nitrite and 0.20 ± 0.05 mg 1^?1 of nitrate were found in Venice lagoon water.     

Simplex Optimisation of a Flow Injection Analysis (Fia) System to Determine Rare Earth Elements (Ree) with Arsenazo III

ABSTRACT

A Flow Injection Method (FIA) for the determination of Rare Earth Elements (REE) in mixed solutions is described and the parameters involved are optimised mathematically by a modified simplex method (MSM). The performance of the system permits the determination of REE from solutions with pH's ranging from 0 to 6. A linear calibration range of up to ca. 30 mg L^?1 for an injection volume of 70 μL and a concentration of Arsenazo III equal to 1.22 mM is achieved representing a tenfold increase over previously reported values. The detection limit of the method is 0.70 mg L^?1 for all the elements studied except Yb which is less sensitive (1.27 mg L^?1). In the case of Yb, an increase in the linear range of up to ca. 40 mg L^?1is achieved. The FIA method can be applied in the analysis of mixtures containing different pairs of REE elements with a relative error of less than 5%.     

An improved procedure for phosphorous fractionation in plant materials exploiting sample preparation and monosegmented flow analysis

Sample treatment procedures were evaluated for fractionation of phosphorous in plant materials (determination of organic and inorganic, soluble and insoluble fractions). The procedures aimed the conversion of different species into orthophosphate, minimizing time, reagent amounts and waste generation. A monosegmented flow system with multicommutation was developed for the spectrophotometric determination of orthophosphate by the molybdenum blue method. Linear response within 0.5 and 25.0 mg L^− 1 P, detection limit of 24 μg L^− 1 P (99.7% confidence level), coefficient of variation of 3.5% (n = 10) and sampling rate of 38 measurements per hour were estimated. Each determination consumes 5.0 mg ascorbic acid and 0.60 mg of ammonium molybdate. Total phosphorous determination can be carried out after microwave-assisted acid digestion by employing 100 mg of plant material and 500 μL of concentrated HNO₃. Extraction of soluble phosphorous can be carried out with water by stirring for 10 min and organic soluble phosphorous can be determined either after microwave-assisted acid digestion or photodegradation in the presence of ammonium persulfate in acid medium. The results for the different fractions agreed with those obtained by ICP OES at the 95% confidence level.     

Comparison of four chromogenic reagents for the flow-injection determination of aluminum in water

Pyrocatechol violet (PCV), aluminon, eriochrome cyanine R (ECR) and eriochrome cyanine R with cetyltrimethylammonium bromide (ECR/CTA) are compared as chromogenic reagents for the flow-injection determination of aluminium in water. The detection limit of the ECR/CTA method is 1 μg Al 1^?1. The detection limits of the PCV and ECR methods are 5 μg Al 1^?1. The aluminon method is the least sensitive, with a detection limit of 50 μg Al l^?1. Interference from iron, fluoride, phosphate and the acidity of the sample were investigated. The interference from iron is suppressed by hydroxylammonium chloride/1,10-phenanthroline in the PCV and ECR/CTA methods at concentrations less than 5 mg Fe l^?1. In the ECR and aluminon methods, iron <5 mg l^?1) is masked by ascorbic acid. Fluoride at <0.2 mg l^?1 can be tolerated in all methods. The aluminon method can tolerate up to about 500 mg l^?1 in the three other methods. All methods are sensitive to changes in acidity of the samples; the acidity should be 0.08–0.12 M HCl.     

A multi-pumping flow system with on-line photochemical conversion and improved sensitivity for phosphorus fractionation in freshwaters

A flow-based procedure with solenoid micro-pumps was developed for phosphorus fractionation (dissolved organic and inorganic phosphorus) in freshwaters. The spectrophotometric detection was based on the formation of molybdenum blue and the organic species were on-line photo-converted to orthophosphate. The analytical response was linear within 10 and 75?µg?L^?1 with a detection limit of 2.0?µg?L^?1 (99.7% confidence level). Coefficient of variation of 1.8% (50?µg?L^?1 P, n?=?20) and sampling rate of 40 determinations per hour were achieved. Per determination, 160?µg (NH₄)₆Mo₇O₂₄, 10?µg SnCl₂, 640?µg K₂S₂O₈ and 10?mg NaOH were consumed, generating 2.0?mL of waste. Slopes of analytical curves obtained for four different organic phosphorus species agreed with those obtained for orthophosphate, indicating quantitative conversion. The results for freshwater samples agreed with those obtained by the AOAC reference procedure at 95% confidence level. The organic matter did not interfere in the photo-oxidative process. The proposed procedure is a fast and environmentally friendly alternative for the phosphorus fractionation in freshwaters.     

Multi-pumping flow system for the determination of dissolved orthophosphate and dissolved organic phosphorus in wastewater samples

A multi-pumping flow system (MPFS) for the spectrophotometric determination of dissolved orthophosphate and dissolved organic phosphorus in wastewater samples is proposed. The determination of orthophosphate is based on the vanadomolybdate method. In-line ultraviolet photo-oxidation is employed to mineralise organic phosphorus to orthophosphate prior to detection. A solenoid valve allows the deviation of the flow towards the UV-lamp to carry out the determination of organic phosphorus.Calibration was found to be linear up to 20 mg P L⁻¹, with a detection limit (3s_b/S) of 0.08 mg P L⁻¹, an injection throughput of 75 injections h⁻¹ and a repeatability (R.S.D.) of 0.6% for the direct determination of orthophosphate. On the other hand, calibration graphs were linear up to 40 mg P L⁻¹, with a detection limit (3s_b/S) of 0.5 mg P L⁻¹, an injection throughput of 11 injections h⁻¹ and a repeatability (R.S.D.) inferior to 2.3% for the procedures involving UV photo-oxidation.     

Selective flow-injection determination of residual chlorine at low levels by amperometric detection with two polarized platinum electrodes

Flow-injection amperometry with two polarized platinum electrodes is used for the determination of residual chlorine based on the oxidation of iodide. Interferences of iron(III), copper(II), nitrite and atmospheric oxygen are eliminated in the proposed procedure. The detection limit for residual chlorine is 2 μg l^?1 at a sampling rate of 120 h^?1; linear calibration graphs are obtained up to 0.8 mg 1^?1. A method for the simultaneous flow-injection determination of residual chlorine and copper(II) is also proposed.     

Spectrophotometric determination of Chromium(VI) using cyclam as a reagent

A simple, rapid, sensitive, and inexpensive method for spectrophotometric determination of chromium(VI), based on the absorbance of its complex with 1,4,8,11-tetraazacyclotetradecane (cyclam) is presented. The complex showed a molar absorbtivity of 1.5?×?10⁴?L?mol^?1?cm^?1 at 379?nm. Under optimum experimental conditions, a pH of 4.5 and 1.960?×?10³?mg?L^?1 cyclam were selected, and all measurements were performed 10?min after mixing. Major cations and anions did not show any interference; Beer's law was applicable in the concentration range 0.2–20?mg?L^?1 with a detection limit of 0.001?mg?L^?1. The standard deviation in the determination is ±0.5?mg?L^?1 for a 15.0?mg?L^?1 solution (n?=?7). The described method provides a simple and reliable means for determination of Cr(VI) in real samples.     

Vergleichende untersuchungen zur titrimetrischen,photometrischen und ionen-chromatographischen hydrogencarbonat-bestimmung in trink-und mineralwässern: A comparison of titrimetric,spectrophotometric and ion-chromatographic methods for the determination of hydrogencarbonate in drinking and mineral waters

A photometric method for hydrogencarbonate determination in various natural waters is presented, based on measurements with methyl red. Accuracy of the results is demonstrated by comparison with titrimetric and ion-chromatographic methods. The photometric method is suitable for contents in the range of 1–2000 mg l^?1. The linear range of the continous flow method varies form 6–60 mg l^?1 to 12–90 mg l^?1 depending on conditions.     

Field determination of fluoride in drinking water using a polymeric aluminium complex of 5-(2-carboxyphenylazo)-8-hydroxyquinoline impregnated paper

A simple field method which allows the determination of fluoride in drinking water with a small handheld instrument called Arsenator was developed. Arsenator is a commercially available instrument which was used successfully for reliable determination of arsenic. In the proposed method the functionality of the Arsenator which is based on a photometric measurement of a spot on the reagent paper is expanded to analyse fluoride. A polymeric aluminium complex of 5-(2-carboxyphenylazo)-8-hydroxyquinoline (LH₂) has been prepared as a new specific reagent for fluoride. Job's method of continuous variation was adopted for the determination of the composition of the coloured complex, which was further characterized by UV-VIS spectroscopic studies. The molar absorptivity of the complex formation is 8.48?×?10³?L?mol^?1?cm^?1 at 410?nm. The coloured complex reacts with fluoride on an impregnated paper where its colour changes are dependent on the concentration of fluoride in water samples. The change in the colour was measured using the Arsenator. The method allows a reliable determination of fluoride in the range 0.3 to 2.0?mg?L^?1. Further spectophotometric determinations of fluoride in drinking water were also studied. The determination is based on the reaction of aluminium complex with fluoride in the examined samples. Beer's law is obeyed in the range 0.3 to 2.0?mg?L^?1 of fluoride at 495?nm. Sensitivity, detection limit and quantitation limit of the method were found to be 0.251?±?0.007?µg^?1?mL, 0.1?mg?L^?1 and 0.3?mg?L^?1, respectively. The optimum reaction conditions and other analytical conditions were evaluated. The effect of interfering ions on the determination is described. There is no interference by nitrate or chloride. Sulphate interfered only at high concentrations which are not expected in drinking water.     

Sequential injection spectrophotometric determination of orthophosphate in beverages, wastewaters and urine samples by electrogeneration of molybdenum blue using tubular flow-through electrodes

A novel and automated sequential injection procedure is proposed for the spectrophotometric determination of orthophosphate without requiring unstable chemical reducing species used in the classical molybdenum blue method. The flowing methodology is based on the on-line generation of the detectable species by electrochemical reduction of the 12-molybdophosphoric acid complex using a stainless steel tubular flow-through working electrode. The established method is linear up to 20 mg/l P, with coefficients of variation (n=10) of 2.4 and 1.8% for 2.0 and 10 mg/l P, respectively. The versatility of the sequential injection method to analyse samples containing high orthophosphate levels has been demonstrated by the implementation of a dilution chamber as well as flow-reversal techniques, yielding relative standard deviations (n=17) better than 2.0% for standards containing 200 and 800 mg/l P. The proposed analyser features an extremely wide dynamic range (viz., 0.3-800 mg/l) as well as improved tolerance to silicate interference, so that Si/P ratios higher than 50 are tolerated at the 5% level. Electrochemical conditions, reagent concentrations and physical variables have been thoroughly investigated. The method has been applied to the determination of orthophosphate in wastewaters as well as beverages and biological samples containing high concentrations of the target analyte. The t-test comparison of the means for the developed sequential injection system with electroreduction and both the molybdenum blue classical spectrophotometric batch procedure and inductively coupled plasma-optical emission spectrometric detection selected as external reference methods revealed that there is no evidence of significant differences between the obtained results at the 95% confidence level.     

Application of microwave-assisted micellar extraction combined with solid-phase microextraction and high-performance liquid chromatography with UV detection for the determination of organochlorine pesticides in different mud samples

Abstract

A sequential injection analysis method for the simultaneous spectrophotometric determination of phosphate and silicate has been developed. The method is based on the different reaction rates of the heteropolymolybdate formation reactions. Concentrations within the range 0.026—0.485 mmol P l^?1 and 0.125—2.848 mmol Si l^?1 have been determined at a frequency of 30 samples per hour. An R.S.D. of 2.1% was obtained for 0.162 mmol P l^?1 and of 1.1% for 1.424 mmol Si l^?1. The method was found to be suitable for the determination of phosphate and silicate in wastewater.     

Extraction Spectrophotometric Determination of Vanadium in Industrial Waste Water

A new and simple extraction spectrophotometric method for the determination of vanadium(V) with KIO₄, N‐phenylbenzohydroxamic acid (PBHA) and crystal violet (CV), in industrial waste water samples is described. It is based on the extraction of mixed‐ligand complex V(V)‐IO₄^? ‐PBHA‐CV⁺ into chloroform solution over 2‐7 MHC1. The molar absorptivity of the complex is (7.20) × 10³1 mol^?1 cm^?1 at λ_max 535 nm. The detection limit of the method is 44 μg 1^?1 V. The linearity of the calibration curve is followed up to 6 μgmL^?1 in the organic solution with slope, intercept and correlation coefficient of 1.34 × 10^?1, 6.7 × 10^?3 and +0.99, respectively. This method enhances the sensitivity of the conventional PBHA method for the determination of vanadium, and is free from interferences of other metal ions commonly associated with vanadium. The method has been successfully tested for the determination of V in the industrial waste water samples.     

Determination of methylmalonic acid after diazonium derivatization by high-performance liquid chromatography

The use of a single prederivatization step in conjunction with high-performance liquid chromatography (h.p.l.c.) is described for the determination of methylmalonic acid (MMA). The method is based on the reaction of MMA and 4-diazobenzenesulfonic acid, which produces a derivative that has a molar absorptivity of about 9 × 10³ l mol^?1 cm^?1 at 353 nm. The derivatization reaction is optimized for various parameters. A reagent concentration of 3.3 mM at a reaction pH of 4.6 and a temperature of 100°C are optimal. The reaction product is separated from the excess of reagent and other interfering components by using a polystyrene-divinylbenzene column and a highly aqueous mobile phase. After a simple clean-up step, it is possible to quantify MMA in urine at about 0.8 mg l^?1 with linear response up to 32 mg l^?1.     

Spectrophotometric Determination of Copper(II) as the Azide Complexes,in the Presence of Iron(III) Cations

Abstract

A method for the spectrophotometrio determination of copper(II), in the presence of iron(III) cations (excess), was stablished. The masking of iron is made with sodium fluoride salt in 50 % (v/v) water/acetone medium. In the recommended conditions, absorbances for cupric complexes are measured at 435 nm where molar absorptivity is 6.00 × 10³ 1 mol^?1 cm^?1.

The stable ayetern obeys Beer's law and is suitable for the copper determination in concentration range from 2.0 to 9.0 mg 1^?l. The iron(III) ion interference (until ca. 600 mg 1^?l) can be completely suppressed. The influence of diverse ions and several others factore were studied.

The results show that copper(II) can be accurately determined by azide apectrophotometric method, if the samples were suitablely treated by the recommended procedure.     

Determination of uranium using a flow system with reagent injection. Application to the determination of uranium in ore leachates

The determination of uranium by a flow system with reagent injection is based on the reaction of U(IV) with Arsenazo III in 3.6 M HCl; U(IV) is generated by reduction of uranyl ion in a lead reductor minicolumn installed in the sample channel of the manifold. The interference effect caused by several ions is studied. The calibration graph is linear up to 1.0 × 10^?5 M (2.4 mg l^?1) and the detection limit is 2.8 × 10^?8 M (6.6 μg l^?1). The modification of the manifold by including a second valve to by-pass the reducing column allows the measurement of the difference in peak heights, which makes the method specific for uranium.     

Flow-injection technique for the determination of low levels of phosphorus in natural waters

An inexpensive flow-injection instrument for determining low concentrations of dissolved reactive phosphorus in natural waters is reported. The unique feature is the use of an inexpensive detector consisting of a flow cell and a simple photometer that incorporates a super-bright light-emitting diode as the source and a photodiode as the detector. The tin(II) chloride-molybdate method was optimized using a modified simplex optimization method. Silicate interference up to 5 mg Si l^?1 was removed by addition of 0.10% (w/v) tartaric acid. Using the tartaric acid-modified optimized reagents, a detection limit of 0.6 μg P l^?1 was achieved. The method was linear over the range 0–100 μg P l^?1 with an excellent precision (r.s.d. 2.9% at 2.0 and 0.5% at 50 μg P l^?1). An in-line pre-concentration anion-exchange column was used to obtain an even lower detection limit of 0.1 μg P l^?1 and applied to the analysis of real samples.     

Continuous flow extraction of indium with bis(2-ethylhexyl)phosphoric acid in 4-methylpentane-2-one coupled on-line with flame atomic absorption spectrometry

Extraction in liquid-liquid segmented flow is used for preconcentration of indium from dilute nitric acid solutions into bis(2-ethylhexyl)phosphoric acid dissolved in 4-methylpentane-2-one. The extraction setup is coupled on-line with flame spectrometry to give a fully mechanized system. The detection limit of the method is 0.03 mg l^?1, the calibration plot is linear up to 1.75 mg l^?1. Repeatability is 1.5% RSD measured at 1 mg l^?1. Sample throughput is 60 h^?1.     

Spectrophotometric determination of chloride in non-polar media by the mercury(II) thiocyanate reaction

A simple, rapid and accurate method for the spectrophotometric determination of chloride in non-polar media is described. The method is based on the well-known reaction of mercury(II) thiocyanate with chloride to release thiocyanate, which then reacts with iron(III). The optimum concentrations of reagents for the determination of chloride in 2,2,4-trimethylpentane (iso-octane) and cyclohexane are reported. The molar absorptivity of the complex at 505 nm is 5120 ± 200 dm³ mol^?1 cm^?1 for iso-octane and 5340 ± 340 dm³ mol^?1 cm^?1 for cyclohexane. Beer's Law is obeyed in the range 2 × 10^?7–2 × 10^?5 mol dm^?3 (0.01–1 mg l^?1) chloride.