Off-Line and On-Line Preconcentration Techniques for the Determination of Phenylureas in Freshwaters

Abstract

Phenylurea herbicides are analysed by reversed-phase liquid chromatography using UV detection at 244 nm after a concentration step in order to determine ppb or sub-ppb levels in drinking and river waters. With an average UV detection limit of 5 ng, a 500 ml sample volume is necessary to reach the 10 ppt level for spiked LC grade water samples and enables easy determination of concentrations below the ppb level for river water samples. Off-line and on-line methods are compared for the concentration step. Off-line concentration consists in a liquid sorption on n-octadecyl silica (C18) and elution by a suitable organic solvent. Polar phenylureas have low retention volumes on C18 silica and consequently the length of the concentration column has to be 10 cm to concentrate them at the ppb level from 100 ml of water and longer for lower levels of detection. Nevertheless, we show that increasing the size of the concentration column does not improve the limits of detection because of the numerous interferences also concentrated when percolating high volumes of water. On-line technology can be used only with short precolumns and requires a sorbent with a great retention for phenylureas. The copolymer-based PRP-1 is found to be an excellent sorbent and it is then possible to apply on-line precolumn technology with preconcentration through two precolumns (10 × 21 mm ID) in series, the first one being packed with C18 silica and the other with the PRP-1 polymer. Interfering compounds are then trapped onto the first precolumn acting as a filter and common phenylurea-breakthrough volumes on the PRP-1 precolumn are higher than 500 ml. Knowing the amounts preconcentrated on both precolumns and using UV and electrochemical detection help the identification of phenylureas in river water.     

Optimization of An On-Line Precolumn Preconcentration Method for the Determination of Polycyclic Aromatic Hydrocarbons (PAHs) in Water Samples (River and Sea Water)

Abstract

A new on-line precolumn preconcentration method for the determination of EPA priority pollutants (PAHs) in river and sea water has been developed. The retention time for each PAH in the precolumn has been determined for several percentages of organic solvent (acetonitrile) in the sample. This is very important because recoveries show a great dependence on this parameter.

The proposed procedure, combined with HPLC and spectrofluorimetric detection, reaches very low detection limits (subnanograms per liter) and it has been applied to river and sea water samples with good results.     

High Performance Liquid Chromatographic Analysis for Free Valine in Plasma

Abstract

A precolumn derivatization method is presented with the use of a fluorescent derivative, 1-dimethylaminonaphhalene-5-sulfonyl-chloride, dansyl chloride, for the detection of free valine in plasma. Dansylated amino acids were determined in deproteinized samples by reverse-phase liquid chromatography. The level of detection is 100 femtoraoles (10^?15). Sample preparation required precipitation of proteins with trichoroacetic acid and removing the excess acid with water saturated ether. The deproteinized sample was adjusted to pH 9.0 and reacted with dansyl chloride. The dansylated products were detected by ultraviolet and fluorescence spectrometry. Elution time for valine subsequent to injection is 25 minutes, while the total assay requires less than 50 minutes.     

Organic-Phase Enzyme Electrode for the Determination of Phenols in Olive Oils

Abstract

A rapid procedure for determining phenols in olive oils, based on an organic-phase enzyme electrode, is described. Direct assays are performed in chloroform solutions which support the tyrosinase activity. This class (phenol)-specific enzyme strongly adheres to the surface of the graphite transducer. The resulting wall-jet detector offers effective flow injection operation, with a detection limit of 4×10^?7 M (0.8 ng) phenol and sample frequency of 60 h^?1. Applicability to olive-oil samples of different origins is illustrated.     

Electrocatalytic Phenol Oxidation on Mixed Pt‐RuO2 Nanoparticle Modified Electrode

Abstract

Nanoscale Pt/RuO₂ colloid with carbon paste support was synthesized and used to prepare a modified electrode for phenol detection. The results showed that the Pt/RuO₂ catalyst has high activity for electrooxidation of phenol with reduced intermediate polymerization due to its significantly low potential for phenol oxidation. The detection limit was as low as 10^?9 mol L^?1 for the polishable Pt/RuO₂/C paste electrode with good reproducibility.     

Photometric Detection Inside the Stream of Sample Sheath Fluid

Abstract

Photometric detection with continuous feed of reagent into the centre of sample flow is described. Performance characteristics of this technique were tested at models without and with chemical reaction. Linear calibration curves were obtained for methylorange (5 x 10^?6 - 1 x 10^?4 M) and for ammonia reaction with the Nessler's reagent (6 x 10^?6 6 x 10^?4 M). The technique was applied for the determination of ammonia in drinking water. In this case, the preconcentration step was necessary.     

Solid-Phase Extraction and Capillary Gas Chromatographic Determination of Triazine Herbicides in Water

Abstract

A facile and efficient method is described for the determination of trace quantities of triazine herbicides, terbutryn, prometryn and ametryn in water. The procedure involved preconcentration of water samples by sorption on chromatographic grade silica gel particles with chemically modified surface, being covalently bonded with a nonofunctional C₈H₁₇ group. This was followed by solvent desorption with 2-propanol. The determinative step was achieved by capillary gas chromatography on Supelcowax-10 fused silica column using a nitrogen-phosphorus detector. The limit of detection was 0.1 μg-10 μgL^?1.     

Trace Enrichment and HPLC Analysis of Chlorophenols in Environmental Samples,Using Precolumn Sample Preconcentration and Electrochemical Detection

Abstract

A HPLC method has been developed for trace analysis of chlorophenols in the 0.2–2 ppb range from spiked water samples. Simple liquid-liquid extraction followed by on-line preconcentration of total mono- and dichlorophenols has been performed using a divinylbenzene-styrene copolymeric sorbent (PRP₁) as packing material for the precolumn. The chlorophenols have been eluted from the precolumn on an analytical column (5μm LiChrosorb RP-18, 12.5 cm × 4 mm) by use of a switching valve system followed by separation. Detection was carried out with an electrochemical detector. The linearity of the detector response has been proved over two orders of magnitude. The detection limit of chlorophenols by means of the electrochemical method is in the lower picogram range. The recoveries of the isomeric chlorophenols from spiked river water samples having initial concentrations of 2ppb are usually 70–90%. The procedure has been applied to drinking water and river water.     

Selective Preconcentration and Ion Chromatography of Trace Lead(II) in Environmental Samples Using a Porous Graphitic Carbon Column

Abstract

Highly selective ion analysis of sub-ppm Pb(II) on a porous graphitic carbon (PGC) column, is described using ion chromatography with acidified aqueous mobile phases, post-column detection using PAR and spectrophotometric detection. Sensitivity is enhanced by on-line preconcentration of the metal prior to the chromatography using one millilitre injection volumes applied to a calix[4]arene-tetrahydroxamate based chelating precolumn. The method is applied to water samples collected from a river subjected to an industrial effluent discharge and results obtained compare favourably with those obtained using flame atomic absorption spectroscopy.     

Green synthesis of soluble polyphenol: oxidative polymerization of phenol in water

Abstract

The simple stirring of phenol with an oxidant in water provided a novel green way to synthesize soluble polyphenol. The soluble polyphenol obtained had a high poly(phenylene oxide) unit ratio, poly(phenyleneoxide)/poly(phenylene)=ca. 80/20. Additionally, the insoluble fraction was identified as a poly(phenyleneoxide), which has a crosslinking point for every 5.5×10³ molecular weight. These results suggest that oxidative polymerization in water can be run in a manner to control the coupling selectivity of phenol. Both the soluble polyphenol and the insoluble fraction showed a high thermal stability. Oxidative polymerization in water provides the potential for a formaldehyde-free and regioselected soluble poly(phenyleneoxide) from phenol.     

Electrochemical Detection of Phenylurea Herbicides in Liquid Chromatography

Abstract

This paper describes the electrochemical detection of ten phenylurea herbicides after on-line trace enrichment on a small C18 precolumn and liquid chromatography on a C18 analytical column. The method presented shows sub-ppb sensitivity in surface water samples without extensive sample pretreatment. Electrode contamination occurs but does not seriously interfere in the routine analysis of such samples. Selective determination (at 1. 0 V) of metoxuron in the presence of other phenylureas allows the detection of 30 ppt of the herbicide in surface water.     

Use of cotton as a sorbent for on-line precolumn enrichment of polycyclic aromatic hydrocarbons in waters prior to liquid chromatography determination

Using cotton as a solid-phase extraction sorbent of the precolumn, an on-line coupled precolumn preconcentration-liquid chromatography system with fluorescence detection was developed for the determination of PAHs in aqueous samples. Four PAHs including fluorene, phenanthrene, fluoranthene and benzo[k]fluoranthene were preconcentrated by a precolumn packed with 30 mg of absorbent cotton and then separated by C₁₈ analytical column. When 100 ml of sample was enriched, the proposed procedure provided detection limits in the range of 0.5-57 ng l⁻¹. Several water samples spiked with PAHs were analyzed with recoveries in the range of 92-119% at spiking level of 100 ng l⁻¹ for fluorene, phenanthrene and fluoranthene, and 10 ng l⁻¹ for benzo[k]fluoranthene, respectively.     

Flow-Injection Biamperometry of Phenol

ABSTRACT

A simple and rapid method determination of phenol is described, using a bromination reaction and biamperometric detection. The method is based on measurements of the intensity of current passing through two identical inert electrodes giving the concentration of phenol in samples. The sample is injected into a stream of carrier and merged with a stream of acidic bromine solution which brominates phenol in the reaction coil. A linear relationship between peak height and phenol concentration is observed in the range of 0.05 to 8 μg ml^?1 of phenol. The relative standard deviation was 2.8% for analysis of 5μg ml^?1 phenol and the sampling rate was 70 h^?1     

Quantitative Analysis of Terbutaline (Bricanyl®) in Human Plasma with Liquid Chromatography and Electrochemical Detection Using On-Line Enrichment

Abstract

A liquid chromatographic method with electrochemical detection (LC-EC) has been developed for the quantitative analysis of terbuta-line in the range 5–50 pmole ml^?1 of human plasma. Terbutaline is isolated from 2 ml of plasma on an ion-exchange column and the eluate is concentrated on a hydrophobic precolumn on-line in the chromatographic system. The precolumn is then back-flushed for further separation onto a hydrophobic analytical column. The mobile phase is a methanol-aqueous buffer to which sodium perchlorate is added to achieve resolution from interfering peaks. A glassy carbon electrode is used for detection. Comparison has been made with gas chromatography-mass spectrometry (GC-MS) to examine the accuracy of the method.     

Adsorptive Voltammetric Measurement of Trace Level of Iron(III) with 4–(2–Pyridylazo) Resorcin

Abstract

The polarographic behavior of the complex of iron–4– (2–pyridylazo) resorcin(PAR) was studied. In HAc– NaAc– EDTA buffer solution, the complex can be adsorped on a hanging mercury drop electrode giving a sensitive adsorptive complex reduction peak with a peak potential at -0.36V(vs. SCE). Optimum experimental conditions were found by the use of 0.08mol/L HAc, 0.06mol/L NaAc, 5.0 × 10^?3mol/L EDTA and 1.0 × 10^?5mol/L PAR. With preconcentration for 60s, the derivative peak height of the complex compound is linearly proportional to the concentration for Fe in the range from 1.0 × 10^?9mol/L to 1.0 × 10^?7mol/L. For a 2–min pre–concentration time, the detection limit found was 2.0 × 10^?10mol/L. This method has high sensitivity and selectivity. It has been applied to the determination of trace iron in food and water samples without any pre–separation step.     

High Performance Liquid Chromatographic Determination of Amino Acids in Biological Samples by Precolumn Derivatization with O-Phthaldialdehyde

Abstract

A suitable gradient system has been developed for rapid analysis of amino acids in biological samples using O-phthaldialdehyde as a precolumn derivatizing agent and fluorescence detection. Resolution of 21 amino acids has been accomplished with 3 μm Ultrasphere ODS column by using a multi-step gradient system of two solvents (0.1M sodium acetate, pH 7.2/methanol:tetrahydrofuran) in less than 1 hour. Within-assay and between-assay coefficients of variation of retention times and fluorescence yield show good reproducibility. The fluorometric detection response is linear from 25 to 500 pmoles with a minimum detection limit of less than 1 pmol. High resolution, rapid analysis and high sensitivity of this method facilitates amino acid analysis in samples of less than 1 mg of tissue.     

Detection of Oxidase Generated Hydrogenperoxide by a Solid State Peroxyoxalate Chemiluminescence Detector

Abstract

The compatability of a solid state peroxyoxalate chemiluminescence detector for hydrogen peroxide with an immobilized oxidase reactor is investigated. As a model system glucose oxidase immobilized by electrostatic forces on an ion-exchanger or chemically bonded to glass beads were chosen. The former support is less suitable for immobilization of oxydases due to strong retention of hydrogenperoxide on the ion exchanger.

The relatively little flow dependence of these systems renders them suitable for low-cost manual sample injection monitors as well as in a flow injection analyses (FIA) mode with low-cost pumping systems. The system was operated with 80% acetonitrile water solutions. A detection limit of 8 × 10^?7M of glucose was achieved in directly injected samples.

Enzymes more sensitive to organic solvents can be operated with pure water and adjustment for optimal chemiluminescence condition is achieved with a make-up flow prior to detection. A detection limit of 5 × 10^?8M glucose is achieved under these conditions. The feasability of this approach to other oxidase based monitors and to detection in liquid chromatography is discussed.     

Determination of Trace Manganese by Adsorption Voltammetry

Abstract

In a solution containing 0.005M borax medium (PH= 8? 10). 0.03% ascorbic acid and 0.001% gelatin, a fine sensitive adsorptive reduction peak of manganese appeared at ?1.53v (vs.SCE) on a hanging mercury electrode by fast speed scanning voltammetry. The derivative peak current is directly proportional to the concentration of manganese in the range from 1.0×10^?8M to 2.0×10^?6M. The detection limit is 3.0×10^?9M. Using this method, we have successfuly determined tracesof Mn in water and strawberry samples.     

Thermal Lens Spectroscopy for Quantitative Determination of a Cu(II) Complex With an 8-Aminoquinoline Derivative in Tap Water and Mining Wastewater Samples Using a Dual Beam Technique

Abstract

This article describes the quantitative determination of Cu(II) using thermal lens spectrometry. The chromogenic reaction involving Cu(II) and 5-(4-sulphophenylazo)-8-aminoquinoline in alkaline solution was studied in different experimental conditions such as pH, ligand concentration, methanol volume, and presence of interfering ions. A collinear dual beam set-up has been used for direct quantitation in water samples without a pre-concentration step. The optimized conditions provided a linear calibration in the concentration range from 3.0 to 15.0?×?10^?7?mol L^?1. The detection and quantitation limits were 6.13?×?10^?8? and 2.04?×?10^?7?mol L^?1, respectively. Resultantly, an application to Cu(II) determination in tap water (recovery 99.8–103.3%) and mining (synthetic) wastewater (95.3–98.0%) shows relative SDs ≤ 3.1%. The method is presented as a new alternative for the direct Cu(II) determination in real samples.     

Determining Trace Concentrations of Copper in Water by Cathodic Film Stripping Voltammetry with Adsorptive Collection

Abstract

A technique is presented for the determination of trace concentrations of copper (II) in natural water samples by cathodic stripping voltammetry of a film of copper-catechol complex ions adsorbed on the hanging mercury drop electrode. The peak height of the copper-catechol reduction peak is linearly dependent upon the copper (II) concentration between 10^?10 and 10^?7 M. The detection limit of the technique is below 10^?10 M copper (II) for a collection time of 3 minutes, but the sensitivity can be further increased four-fold by collecting for 15 minutes. The sensitivity is reduced by high concentrations of competing trace metals and of surfactants, which necessitate the use of standard additions to the sample.