Fast low-pressure microwave assisted extraction and gas chromatographic determination of polychlorinated biphenyls in soil samples.

A new technology equipment for low-pressure microwave assisted extraction (usually employed for organic chemistry reactions), recently launched in the market, is used for the first time in environmental analysis for the extraction of commercial technical Aroclor mixtures from soil. Certified reference materials of Aroclor 1260, Aroclor 1254 and Aroclor 1242 in transformer oils were used to contaminate the soil samples and to optimize the extraction method as well as the subsequent gas chromatographic electron capture detection (GC-ECD) analytical method. The study was performed optimizing the extraction, the purification and the gas chromatographic separation conditions to enhance the resolution of difficult pairs of congeners (C28/31 and C141/179). After optimization, the recovery yields were included within the range 79-84%. The detection limits, evaluated for two different commercial polychlorinated biphenyl (PCB) mixtures (Aroclor 1260 and Aroclor 1242) were 0.056 ± 0.001 mg/kg and 0.290 ± 0.006 mg/kg, respectively. The method, validated with certified soil samples, was used to analyze a soil sample after an event of failure of a pole-mounted transformer which caused the dumping of PCB contaminated oil in soil. Moreover, the method provides simple sample handling, fast extraction with reduced amount of sample and solvents than usually required, and simple purification step involving the use of solvent (cyclohexane) volumes as low as 5 mL. Reliability and reproducibility of extraction conditions are ensured by direct and continuous monitoring of temperature and pressure conditions.

Determination of herbicides by solid phase extraction gas chromatography-mass spectrometry in drinking waters.

A solid phase extraction (SPE) method has been optimized for the gas chromatography-mass spectrometry (GC-MS) simultaneous determination of herbicides belonging to the following different families: carbamate (molinate), atrazines (atrazine, propazine, simazine, ametryne, cyanazine, terbutylazine, deethylterbutylazine, deethylatrazine), dinitroaniline (trifluralin, pendimethalin), chloroacetamide (alachlor, metolachlor). Different solid substrates have been compared (C18, cyano, styrene-divinylbenzene, phenyl, graphitic carbon). The type of conditioning and elution solvent, its volume, and the sample flow rate have been considered as variables affecting the recovery yields of the herbicides. The optimized experimental conditions are C18 phase conditioned with 3 mL acetone, loaded with 1L water sample at 5 mL min(-1), and eluted with 3 mL acetone. Good recoveries (included between 79% and 99%) and R.S.D. (included between 2% and 12%) have been obtained for all analytes, except for deethylatrazine whose recovery was 46+/-7%. The recovery of deethylatrazine increases up to 94+/-17% if a non-porous graphitic carbon is coupled to the C18 phase, keeping the other parameters constant as optimized. The optimized method has been successfully checked for the identification and quantitation of the selected herbicides in raw and drinking water samples, with quantitation limits as low as 0.01 microg L(-1), fully in agreement with the current legislation. The method is easily routinable. After development, the method is currently routinely applied for the analysis of herbicides in waters and, up today, more than one thousand samples have been analysed at the "Laboratorio della Società Metropolitana Acque di Torino" (Laboratory of the Municipal Waterworks of Turin) in charge of the control of drinking water quality in Torino.

On-line preconcentration, ion chromatographic separation and spectrophotometric determination of palladium at trace level.

A new method for the determination of Pd by ion chromatography and spectrophotometric detection has been developed. The technique is based on the separation of palladium as PdCl4(2-) by anion exchange and on the detection, at a wavelength of 407 nm, of metal as PdI4(2-) after a post-column reaction with KI. The column used was an IonPac AS4 with HCl and HClO4 eluents. The eluent concentration and composition of post-column reagent were optimised in order to obtain the best separation and sensitivity for Pd. In order to reduce the detection limit, an on-line preconcentration step, has been optimised. The method, as developed, was suitable for palladium determination within a 300 ng/l D.L. value. The method applied to a BCR reference material (CRM 277, estuarine sediment) gave satisfactory results in agreement with the certified value within a D.L. value of 1.3 microg/l for the real sample.

Ion chromatography with inductively coupled plasma mass spectrometry, a powerful analytical tool for complex matrices estimation of Pt and Pd in environmental samples.

A new method for palladium and platinum direct determination in environmental samples is proposed by coupling ion chromatography with quadrupole inductively coupled plasma MS. In order to optimise Pd and Pt separation and to minimise interference from matrix in real samples, several anionic and cationic stationary phases have been compared at different mobile phase compositions. In particular, the effect of acidity and of the addition of oxalic acid to the eluent on separation and detection performance has been studied, and the anion-exchange column AG11 turned out to be more suitable. After chromatographic and mass spectrometer parameter optimisation, several potential interferences and the main quality parameters of the method, according to the Eurachem-CITAC recommendations, were evaluated: the detection limit for Pt was 5 ng l(-1) while the value for Pd was 230 ng l(-1). The method was successfully employed in the determination of platinum group elements in urban road dust and atmospheric particulates and the complete absence of matrix spectral interferences was demonstrated.

Adsorption of heavy metals on Na-montmorillonite. Effect of pH and organic substances.

Clays (especially montmorillonite and bentonite) are widely used as barriers in landfills to prevent contamination of subsoil and groundwater by leachates containing heavy metals. For this reason it is important to study the adsorption of metals by these clays. The sorption of seven metals (Cd, Cr, Cu, Mn, Ni, Pb and Zn) on Na-montmorillonite was studied as a function of pH and in the presence of ligands, forming complexes of different stabilities with the metals of interest. The continuous column method was used as it better simulates natural conditions. The total capacity of Na-montmorillonite towards these metals was determined. The pH variations influence to a higher extent the concentrations of Cu, Pb and Cd in the effluent. Moreover the results suggest that complex formation hinders the sorption of the metals on the clay, with an increasing influence in the order: Mn < or = Pb < or = Cd < or = Zn < Ni < Cu < Cr. The evaluation of the total capacity of Na-montmorillonite shows that this clay is a good sorbent towards all examined metals.

Heavy metals in agricultural soils from Piedmont, Italy. Distribution, speciation and chemometric data treatment.

The distribution and speciation of heavy metals in five agricultural soils of Piedmont Region (north-western Italy) were investigated. Ten metals, namely Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Ti and Zn were considered. Analytical determinations were performed by atomic emission or atomic absorption spectroscopy after microwave sample dissolution in acid solution. Total metal concentrations fit in the typical concentration ranges for unpolluted soils, with the exception of cadmium and lead content in some horizons. The effect of sampling depth on concentrations was discussed. Speciation studies were carried out by applying Tessier's procedure, which allows to subdivide the total metal content into five fractions, representing portions bound to different components of the soil. Moreover, the element labilities in two soils were evaluated by extraction with EDTA. Correlations among the variables and/or similarities among the sampling points were identified by principal component analysis and hierarchical cluster analysis.

Vacancy ion-exclusion chromatography of carboxylic acids on a weakly acidic cation-exchange resin.

In this preliminary study, a new approach to ion-exclusion chromatography is proposed to overcome the relatively poor conductivity detection response which occurs in ion-exclusion chromatography when acids are added to the eluent in order to improve peak shape. This approach, termed vacancy ion-exclusion chromatography, requires the sample to be used as eluent and a sample of water to be injected onto a weakly acidic cation-exchange column (TSKgel OApak-A). Vacancy peaks for each of the analytes appear at the retention times of these analytes. Highly sensitive conductivity detection is possible and sharp, well-shaped peaks are produced, leading to efficient separations. Retention times were found to be affected by the concentration of the analytes in the eluent, and also by the presence of an organic modifier such as methanol in the eluent. Detection limits for oxalic, formic, acetic, propionic, butyric and valeric acids were 0.1, 0.2, 0.3, 0.3, 0.4 and 0.5 microM, respectively, and linear ranges for some acids extended over two orders of magnitude. Precision values for retention times were 0.21% and for peak areas were <1.90%. The vacancy ion-exclusion chromatography method was found to give detection responses four to 10 times higher than conventional ion-exclusion chromatography using sulfuric acid eluent and two to five times higher than conventional ion-exclusion chromatography using benzoic acid eluent.

Effect of ion-exchange site and eluent modifiers on the anion-exchange of carboxylic acids.

The chromatographic behavior of carboxylic acids has been investigated, on three different latex-based anion-exchange columns, in order to define the effect of the ion-exchange site structure on selectivity. The analytical columns produced are characterized by alkyl amines containing zero, one or two hydroxyl groups on the anion-exchange functional site. Divalent carboxylic acids, namely fumaric, maleic, trans-beta-hydromuconic, trans,trans-muconic, oxalic, malonic, succinic, glutaric, adipic, malic, tartaric and mucic acids, have been chosen as test solutes. The performance of the three stationary phases has been studied employing NaOH eluents and has been discussed with respect to the different hydrophilicity of the ion-exchange sites and analytes. Considering on previous results obtained using organic solvents (methanol and acetonitrile) with carbonate eluents on a highly hydrophilic column, the performance of the three exchangers has also been studied using acetonitrile, methanol and n-propanol. The chromatographic behavior was similar for the three columns studied, but the different organic solvents gave variations in selectivity. In order to characterize these differences, particle size measurements of the latices were performed both in pure water and in the presence of each organic solvent studied.

High-performance ion-exclusion/cation-exchange chromatography of anions and cations in acid rain waters on a weakly acidic cation-exchange resin.

A new method for the simultaneous determination of anions (sulfate, nitrate, and chloride) and cations (sodium, ammonium, potassium, magnesium, and calcium) in acid rain waters was investigated using high-performance ion-exclusion/cation-exchange chromatography with conductimetric detection on a separation column packed with a polymethacrylate-based weakly acidic cation-exchange resin in the hydrogen-form and an eluent comprising 1.5 mM sulfosalicylic acid-6 mM 18-crown-6 at pH 2.6, operated at 1.5 ml/min. Effective separation and highly sensitive conductimetric detection for the anions and the cations was achieved in about 14 min. Since the ionic balance (equivalents of anions/equivalents of cations) of acid rain waters of different pH (4.40-4.67) ranged from 0.97 to 0.94, evaluation of the water quality of acid rain was possible. This method was successfully applied to the simultaneous determination of the anions and the cations in acid rain transported from mainland China and North Korea to central Japan monitored by a meteorological satellite data analyzer.

Liquid chromatographic methods for chloral hydrate determination.

Liquid chromatographic methods, based on reversed-phase (RP) and anion-exchange mechanisms, have been developed for chloral hydrate determination. Both methods are preceeded by derivatization of chloral hydrate. For RP separations, different reagents [namely dansylhydrazine and o-(4-nitrobenzyl)hydroxylamine] have been studied, but the best results have been achieved using 1,2-benzenedithiol with UV detection at 220 nm. The anion-exchange method is based on derivatization with NaOH to form sodium formate that is then analyzed by anion-exchange, with suppressed conductivity detection. Derivatization conditions were optimized in order to reach the best yield of reaction. The optimization of the procedure allowed to determine chloral hydrate with detection limits as low as 0.2 microg/l with good linearity and reproducibility. The anion-exchange method was also applied for chloral hydrate determination in a drinking water sample. A preconcentration procedure has also been studied.

Determination of epichlorohydrin by ion chromatography.

In this work we developed a new method for epichlorohydrin determination with suppressed ion chromatography. The technique is based on a reaction between the analyte and sulfur(IV) to form a product with a terminal sulfonate group that can be analyzed by anion-exchange chromatography. The reaction conditions were optimized as a function of temperature, type and concentrations of reagents and pH. Due to the characteristics of the product formed, the columns used were an lonPac AS 11 and AS II-HC with a NaOH eluent. The eluent concentration was optimized in order to achieve a complete separation of epichlorohydrin, chloride and nitrate ions, commonly occurring in drinking waters. In order to improve the detection limits, a preconcentration step, using reversed-phase materials, has been optimized. The method developed was suitable for epichlorohydrin determination in drinking water.

Effect of stationary phase hydrophobicity and mobile phase composition on the separation of carboxylic acids in ion chromatography.

In a previous work, we studied the retention behavior of monovalent and divalent carboxylic acids on a highly cross-linked polystryene-divinylbenzene anion-exchange column (IonPac AS4A-SC) using a carbonate-based buffer, and a retention model was applied to the chromatographic data obtained. In this work we characterized the retention of carboxylates (formic, acetic, propionic, lactic, pyruvic, oxalic, malonic, succinic, fumaric, maleic, tartaric, glutaric, adipic, malic, mucic, trans-beta-hydromuconic, trans,trans-muconic acids) on a column with higher hydrophilicity (IonPac AS11) according to analyte and stationary phase properties, using previously investigated eluent compositions and comparing the retention data obtained. Moreover, the effect of organic modifiers (CH3OH and CH3CN) in the eluent on the retention factors was also evaluated. The chromatographic data obtained on the IonPac AS11 column were fitted by the retention model and allowed one to obtain and to compare ion-specific selectivity constants (parameters of the model) with the ones obtained with the previous column.

Preconcentration of contaminants in water analysis.

Among the environmental areas, in this review attention will be focused on water matrices and both on organic (e.g., pesticides, herbicides, phenols, polycyclic aromatic hydrocarbons), inorganic species and anion pollutants, since these kinds of substances include a wide number of compounds with different physical and chemical properties and different effects on human health. Analytical methods for control of quality of waters are required to be highly specific and possibly highly sensitive for the determination of even low amounts of pollutants. The main problems encountered during the analysis are the separation of matrix components from the pollutants of interest and the achievement of low detection limits. Therefore an overview on different materials and techniques available for sample concentration and/or matrix removal will be provided and discussed according to the chemical characteristics of the pollutant that has to be enriched.

Preconcentration and separation of haloacetic acids by ion chromatography.

A comparative study was made of the chromatographic behaviour of five haloacetic acids (mono-, dibromoacetic and mono-, di-, trichloroacetic acids). The techniques investigated included reversed-phase ion interaction chromatography with UV detection, suppressed and non-suppressed anion-exchange chromatography. The systems are discussed studying the retention as a function of the mobile phase parameters and the stationary phases used (LiChrospher 100 RP-18, IonPac AS9, AS10 and AS11). A preconcentration step, performed on different substrates, namely LiChrolut-EN and activated vegetal carbon, has been optimized in order to reduce the method detection limits. Results obtained for drinking water samples are shown.

Liquid chromatography: a tool for the analysis of metal species.

An overview is presented of classic and more recent applications of liquid chromatography for the analysis of metal species. The different approaches involving ion-exchange, ion-pair, and chelation separation mechanisms are discussed as well as the new philosophy of simply removing interferents before specific detections of metal ions (alkali and alakaline earths, rare earths, heavy and transition metals). New more selective materials enabling difficult separations and studies on multimodal or hyphenated techniques for metal speciation (e.g. arsenic and chromium) are considered.

Carboxylic acids: prediction of retention data from chromatographic and electrophoretic behaviours.

A review of the main results reached in the prediction of retention data of carboxylic acids, inferred by their chromatographic and electrophoretic behaviour, is presented. Attention has been focused on the main separation methods used in carboxylic acids analysis, that is ion-exclusion, anion-exchange, reversed-phase (RP) liquid chromatography and capillary electrophoresis. Papers proposing mechanistic models as well as chemometric and multilayer feed-forward neural network analysis of ion chromatography (IC) and RP chromatographic retention data were reviewed. Principal component analysis, PCA, sequential simplex method and simultaneous modelling of response surfaces through simple nonlinear models (not related to equilibria involved in retention) have been considered. Computer simulations for the prediction of retention data have also been discussed. A quick overlook on the prediction of capacity factors of analytes by less common determination methods such as thin-layer, gas chromatography and supercritical fluid chromatography has also been done.

Flow injection determination of Pb and Cd traces with graphite furnace atomic absorption spectrometry.

The preconcentration and recovery of lead and cadmium traces at ng l(-1) level were evaluated in standard solutions and natural aqueous samples using a FIAS (Flow Injection Atomic Spectrometry) apparatus. The method is based on retention of the complex formed between Pb or Cd and 1,2-dihydroxy-3,5-benzendisulphonic acid (Tiron) on a macroporous anion-exchange resin. The recovery of the analytes was obtained by elution with 0.1 M HCl and their determination was performed by Graphite Furnace Atomic Absorption Spectrometry (GFAAS). The detection limits were 9 and 7 ng l(-1) for Pb and Cd respectively. The effects of sample solution pH and composition and of interfering agents as well as reagent purity are discussed. The technique was applied to the analysis of natural waters.

Evaluation of stability constants of metal complexes with sulphonated azo-ligands.

An ion-exchange procedure is described for the determination of the stability constants for cadmium, copper, nickel and manganese complexes with three sulphonated azo ligands: calmagite, alizarin violet N and palatine chrome black. The results, log K values, show a good agreement with those obtained by a spectrophotometric technique.

Determination of plasma tocopherols by high-performance liquid chromatography with coulometric detection.

An HPLC procedure has been developed for tocopherol determination with coulometric detection in human serum samples. Eluent optimization and foreign peak identification (bilirubin) by mass spectrometry are described. An extraction procedure gave yields around 98% with 1.3% coefficient of variation, and the calibration ranged from 0.1 to 200 mg/l with a correlation coefficient of 0.999. The detection limit achieved for vitamin E was 60 pg (3 ng/ml).