Optimization of the matrix solid-phase dispersion sample preparation procedure for analysis of polycyclic aromatic hydrocarbons in soils: comparison with microwave-assisted extraction.

A fast and simple preparation procedure based on the matrix solid-phase dispersion (MSPD) technique is proposed for the first time for the isolation of 16 polycyclic aromatic hydrocarbons (PAHs) from soil samples. Naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[e]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[a,h]anthracene, benzo[g,h,i]perylene, and indeno[1,2,3-c,d]pyrene were considered in the study. Extraction and clean-up of samples were carried out in a single step. The main parameters that affect extraction yield, such as dispersant, type and amount of additives, clean-up co-sorbent and extractive solvent were evaluated and optimized. The addition of an alkali solution in MSPD was required to provide quantitative recoveries. Analytical determinations were carried out by high performance liquid chromatography (HPLC) with fluorescence detection. Quantification limits (between 0.01 and 0.6 ng g(-1) dry mass) were well below the regulatory limits for all the compounds considered. The extraction yields for the different compounds obtained by MSPD were compared with the yields obtained by microwave-assisted extraction (MAE). To test the accuracy of the MSPD technique, the optimized methodology was applied to the analysis of standard reference material BCR-524 (contaminated industrial soil), with excellent results.

Approaches for the simultaneous extraction of tetrabromobisphenol A, tetrachlorobisphenol A, and related phenolic compounds from sewage sludge and sediment samples based on matrix solid-phase dispersion.

A procedure based on matrix solid-phase dispersion (MSPD) for sample preparation in the analysis of some bromophenols and halogenated bisphenols in sediments and sludges has been developed. For the first time ever, MSPD was applied for the extraction of organic contaminants from sediment and sewage sludge samples. The influence of experimental conditions on the yield of the extraction process and on the efficiency of the built-in cleanup step was thoroughly evaluated. Analysis of the extracts was performed by nonaqueous capillary electrophoresis coupled with photodiode array ultraviolet detection, using large-volume sample stacking injection based on the electroosmotic flow pump as an on-column preconcentration technique. The method was applied to the analysis of real sludges from urban sewage treatment plants, as well as river and marine sediment samples.

Application of matrix solid-phase dispersion in the analysis of priority polycyclic aromatic hydrocarbons in fish samples.

The performance of matrix solid-phase dispersion (MSPD) for the extraction of polycyclic aromatic hydrocarbons (PAHs) in fish tissue is described. The suitability of different solid supports was tested as well as the influence on the extraction efficiency of the natural fat content in samples. Under optimal conditions 0.6-0.8 g of tissue sample, are dispersed with 2 g of octadecylsiloxane (C18) and 0.5 g of anhydrous sodium sulphate and transferred to the top of a polyethylene solid-phase extraction cartridge which already contains 2 g of florisil and 1 g of C18. Cartridges were eluted with acetonitrile. The analysis of the extracts was carried out by high-performance liquid chromatography (HPLC) coupled with fluorescence detection. The proposed method provides detection limits between 0.04 and 0.32 ng/g for the different considered PAHs, below the maximum levels established by the some regulatory bodies for the six PAHs after recent oil spill episodes and European Union regulations. Recoveries over 80% were obtained for all compounds. Accuracy validation was carried out using the US National Institute of Standards and Technology (NIST) SRM 2977 reference material.

Analysis of tetrabromobisphenol A and other phenolic compounds in water samples by non-aqueous capillary electrophoresis coupled to photodiode array ultraviolet detection.

Non-aqueous capillary electrophoresis (NACE) with large-volume sample stacking injection using the electroosmotic flow pump (LVSEP) has been developed for the determination of tetrabromobisphenol A (TBBPA) and other phenolic compounds in environmental matrices. Methanol has been used as run buffer solvent to reduce the electroosmotic flow (EOF). Identification and quantification of the analytes was performed by photodiode array ultraviolet detection. LVSEP-NACE improved sensitivity of the peak height by 90-300-fold. The method developed was applied to the analysis of TBBPA in river water and wastewater samples, using solid-phase extraction (SPE) as sample pretreatment process. The average recoveries of the analytes were in the range of 96-106% and 73-103% for 1 L of river water and 0.5 L of wastewater samples, respectively. When the method was based on off line SPE-LVSEP-NACE, sensitivity was improved by 3300-4500-fold and 1600-2200-fold for river water and wastewater samples, respectively.

Comparative study of aqueous and non-aqueous capillary electrophoresis in the separation of halogenated phenolic and bisphenolic compounds in water samples.

Capillary zone electrophoresis methods, based on either aqueous and non-aqueous solutions as running buffers and UV spectrophotometric detection, have been developed and optimized for the separation of several halogenated phenolic and bisphenolic compounds, suspected or proved to exhibit hormonal disrupting effects. Both aqueous capillary electrophoresis (CE) and non-aqueous capillary electrophoresis (NACE) methods were suitable for the analysis of compounds under study. The separation of the analytes from other 25 potentially interfering phenolic derivatives was achieved with NACE method. Large-volume sample stacking using the electroosmotic flow pump (LVSEP) was assayed as on-column preconcentration technique for sensitivity enhancement. LVSEP-CE and LVSEP-NACE improved peak heights by 5-26 and 16-330 folds, respectively. To evaluate their applicability, the capillary electrophoresis methods developed were applied to the analysis of water samples, using solid-phase extraction as sample pre-treatment process.

Strategic sample composition in the screening of polycyclic aromatic hydrocarbons in drinking water samples using liquid chromatography with fluorimetric detection.

The screening of polycyclic aromatic hydrocarbons in water samples by means of the strategic sample composition (SSC) technique is presented. SSC uses special supersaturated composition matrices to perform sample composition and analysed the results obtained in the analytical determination of these composite samples by means of evolutionary assisted regression procedures providing estimations of the concentration levels of analytes in each individual sample specimen. Here, 12 composite samples were prepared by departing from 26 water sample specimens, five of which were spiked with known amounts of several polycyclic aromatic hydrocarbons (PAHs). These composite samples were analysed by HPLC using fluorescence detection. Concentration levels spiked were, in some cases clearly higher than allowed limits for drinking waters, whereas in other cases are just in the limit or even down these limits. The study shows the ability of SSC to detect the really contaminated samples and guiding the analyst in taking the adequate decisions.

Application of chromatographic and electrophoretic methodology to the speciation of organomercury compounds in food analysis.

Trace metals such as mercury, especially its organic compounds, are an important risk to the environment and to man due to their accumulation in the food chain. For this reason, the routine determination of the very toxic methylmercury, and of other organic and inorganic mercury compounds in marine and land animals, vegetables, fruits and fresh water is of increasing importance in health and environmental control programmes throughout the world. The majority of speciation methods for organomercurials involve a series of fundamental steps for the identification and quantification of samples of biological origin: extraction or isolation from the matrix; derivatisation and concentration; detection; separation of different species of interest and of interference. Each of these steps, as part of the chromatographic analysis of MeHg and of other organomercurials is revised in this study using food samples.

Evaluation of two solid-phase extraction procedures for the preconcentration of chlorophenols in drinking water.

Two off-line concentration procedures for the determination of sixteen chlorophenols in drinking water were developed. One involves acetylation of the samples and their subsequent preconcentration over graphitized carbon black cartridges. In the other, chlorophenols are derivatized following preconcentration over cross-linked styrene-divinylbenzene. The two proposed procedures are compared in terms of chlorophenol recoveries, throughput and breakthrough volume of the cartridges. The acetylated derivatives of chlorophenols are determined highly selectively at the concentration levels established by international legislation using gas chromatography in combination with microwave induced plasma atomic emission spectroscopy.

Determination of phenolic pollutants in drinking water by capillary electrophoresis in the sample stacking mode.

A method for the determination of phenol, chlorophenols and nitrophenols at levels below those allowed by international legislation in water from the public supply is proposed. Ten of the compounds studied are included on the USA Environmental Protection Agency priority list of aquatic pollutants. Samples are concentrated off-line on cross-linked polystyrene and subsequently subjected to capillary electrophoresis using the sample stacking procedure to remove the matrix. The recoveries afforded by the off-line concentration process and the behaviour of the phenols in relation to sample stacking injection were examined.

Speciation of organotin compounds in marine biomaterials after basic leaching in a non-focused microwave extractor equipped with pressurized vessels.

A rapid method for the speciation of butyl- and triphenyltin compounds in marine biotissues is described. A non-focused microwave extractor, operating at a power of 950 W and equipped with 12 pressurized vessels, was used to achieve fast sample leaching with tetramethylammonium hydroxide. The pH of the liquid extract was adjusted to 5. Organotins were ethylated with sodium tetraethylborate, extracted in isooctane and determined by means of a microwave-induced plasma atomic emission detector coupled to a gas chromatograph. The stability of butyl and phenyl compounds, exposed to the microwave energy, was studied as a function of the vessel temperature. The possibility of simultaneous carried-out extractions and the use of microwave to perform the ethylation and extraction of organotin compounds was also studied. The full procedure was validated with certified material NIES-11 and with real samples, by comparison with a classic leaching method using tetramethylammonium hydroxide without microwave.

Determination of chlorophenols in drinking water samples at the subnanogram per millilitre level by gas chromatography with atomic emission detection.

The use of an atomic emission detector following a process of preconcentration of drinking water samples by a factor of 1500:1 allows the highly selective determination of chlorophenols present in samples below the maximum limit of 0.5 ng/ml set by international regulations. The preconcentration of the samples is carried out using 0.25-g commercial graphitized carbon cartridges without the need for sample derivatization prior to solid-phase extraction.

Speciation of organomercurials in marine samples using capillary electrophoresis.

A rapid method for speciation and determination of organomercury compounds in biological samples of marine origin using Capillary Electrophoresis (CE) is reported. Organomercurials were extracted from the samples by means of the classical Westöö procedure thus giving organomercury-cysteine complexes which can be separated from each other by means of CE resulting in effective speciation. Electrophoretic separation was achieved in an open silica capillary tube at 15-18 kV using a 100mM sodium borate buffer (pH 8.35). All mercury species were distinctively separated within 12 min. Results are presented for the analysis of real marine samples and reference materials, and compared with those obtained by the GC commonly accepted procedure.