Ion chromatographic separations of phosphorus species: a review

The aim of this paper is to review recent literature regarding the determination of phosphorus species by ion chromatography (IC), and describe the implementation of new developments in sample treatment and ion chromatography methodology for the analysis of these compounds. Ion-exchange methods using both carbonate/hydrogencarbonate and hydroxide selective columns in combination with self-regenerating membrane and solid-phase-based suppressors enable determination of phosphate down to ppb levels. New technology, particularly on-line electrolytic hydroxide generators and electrolytic self-regenerating suppressor devices, has allowed the use of elution gradients in both carbonate/hydrogencarbonate and hydroxide selective systems, improving sensitivity and reducing total analysis time for samples containing phosphate together with other inorganic anions. In addition to a review of these developments, optimization and application of chromatographic methods using reversed stationary phases and cationic and/or zwitterionic surfactants is also discussed.The objective of most of the IC methods developed for phosphorus species is the determination of phosphate and total phosphorus. Therefore, sample treatment and separation conditions specifically developed for this purpose are also described. In addition, application of IC to the analysis of other inorganic (reduced and condensed) and organic (phytates, alkyl phosphate, and phosphonates) phosphorus species is discussed along with methodology and relevant applications in water analysis and other miscellaneous fields.     

Characterization of winemaking yeast by cell number-size distribution analysis through flow field-flow fractionation with multi-wavelength turbidimetric detection

Yeasts are widely used in several areas of food industry, e.g. baking, beer brewing, and wine production. Interest in new analytical methods for quality control and characterization of yeast cells is thus increasing. The biophysical properties of yeast cells, among which cell size, are related to yeast cell capabilities to produce primary and secondary metabolites during the fermentation process. Biophysical properties of winemaking yeast strains can be screened by field-flow fractionation (FFF). In this work we present the use of flow FFF (FlFFF) with turbidimetric multi-wavelength detection for the number-size distribution analysis of different commercial winemaking yeast varieties. The use of a diode-array detector allows to apply to dispersed samples like yeast cells the recently developed method for number-size (or mass-size) analysis in flow-assisted separation techniques. Results for six commercial winemaking yeast strains are compared with data obtained by a standard method for cell sizing (Coulter counter). The method here proposed gives, at short analysis time, accurate information on the number of cells of a given size, and information on the total number of cells.     

Field amplified sample injection‐capillary zone electrophoresis for the analysis of amprolium in eggs

Veterinary medicines are widely administered to farm animals since they keep animals healthy at overcrowded conditions. Nevertheless the continuous administration of medicines to farm animals can frequently lead to the presence of residues of veterinary drugs in consumption products. Amprolium is a quaternary ammonium compound used in the treatment of coccidiosis. In this paper, a method based on CZE to analyze residues of amprolium in eggs was developed and validated for the first time. Parameters such as electrolyte type, concentration, and pH were optimized. In order to improve sensitivity, field‐amplified sample injection (FASI) was used for in‐line preconcentration after a quick and simple sample treatment based on SPE (Envi‐Carb). During method‐validation studies using egg samples, a matrix interference was found at the migration time of amprolium. This compound was identified as thiamine and confirmed by MSⁿ experiments using CEcoupled to MS (CE‐MS) with an ion‐trap mass analyzer. CZE conditions were reoptimized to separate thiamine from amprolium allowing the quantification of amprolium in eggs at concentrations down to 75 μg/kg, which are far below the MRL‐legislated values.     

Selective pressurized liquid extraction of polybrominated diphenyl ethers in fish

A fast and simple method for the analysis of polybrominated diphenyl ethers (PBDEs) in fish samples was developed using a one-step extraction and clean-up by means of pressurized liquid extraction (PLE) combined with gas chromatography-ion trap tandem mass spectrometry (GC-ITMS-MS). The selective PLE method provided to obtain ready-to-analyse extracts without any additional clean-up step, using a sorbent as fat retainer inside the PLE cell. Several PLE operating conditions, such as solvent type, extraction temperature and time, number of cycles and type of fat retainer, were studied. Using Florisil as fat retainer, maximum recoveries of PBDEs (83-108%) with minimum presence of matrix-interfering compounds were obtained using a mixture of n-hexane:dichloromethane 90:10 (v/v) as solvent, an extraction temperature of 100 °C and a static extraction time of 5 min in combination with three static cycles. Quality parameters of the method were established using standards and fish samples. Limits of detection and quantification ranged from 10 to 34 pg g⁻¹ wet weight and between 34 and 68 pg g⁻¹ wet weight, respectively. In addition, good linearity (between 1 and 500 ng ml⁻¹) and high precision (RSD % < 15%) were achieved. The method was validated using the standard reference material SRM-1945 (whale blubber) and was then applied to the analysis of PBDEs in fish samples.     

Absence of Gradients and Nernstian Equilibrium Stripping (AGNES) for the determination of [Zn] in estuarine waters

Zinc (Zn) has been classified as a “Specific Pollutant” under Annex VIII of the EU Water Framework Directive by two thirds of the EU member states. As a result, the UK Environmental Quality Standard (EQS) for Transitional and Coastal (TrAC) Waters has been reduced from 612 nM to 121 nM total dissolved Zn. It is widely accepted that the free metal ion ([Zn²⁺]) is the most bioavailable fraction, but there are few techniques available to determine its concentration in these waters. In this work, Absence of Gradients and Nernstian Equilibrium Stripping (AGNES) has been applied, for the first time, to determine [Zn²⁺] in estuarine waters. The AGNES method had a mean RSD of ±18%, a (deposition time dependent) limit of detection of 0.73 nM and a [Zn²⁺] recovery of 112 ± 19% from a certified reference material (BCR-505; Estuarine Water). AGNES results for 13 estuarine samples (salinity 0.1–31.9) compared well (P = 0.02) with Competitive Ligand Exchange Cathodic Stripping Voltammetry (CLE-AdCSV) except for one sample. AGNES requires minimal sample manipulation, is unaffected by adsorption of interfering species at the electrode surface and allows direct determination of free zinc ion concentrations. Therefore AGNES results can be used in conjunction with ecotoxicological studies and speciation modelling to set and test compliance with water quality standards.     

Synthesis of monoclinic KGd(WO4)2 nanocrystals by two preparation methods

The monoclinic crystalline phase of KGd(WO₄)₂ is a well-known solid-state laser host. The present article describes how monoclinic nanocrystals of KGd(WO₄)₂ are synthesized by two different methodologies: the sol–gel modified Pechini method and femtosecond pulsed laser ablation of bulk material in deionized water. Transmission Electron Microscopy images show KGdW nanocrystals between 15 and 100 nm for both methods. The nanocrystals are studied by X-ray powder diffraction (XRD) in order to identify the crystalline phase and to refine the unit cell parameters. For the sol–gel modified Pechini method, differential thermal analyses and XRD techniques were also used to optimize the method of preparation.     

Evaluation of different clean-up procedures for the analysis of heterocyclic aromatic amines in a lyophilized meat extract

Along with other mutagenic and carcinogenic contaminants in foods such as aflatoxins, and polycyclic aromatic hydrocarbons, heterocyclic aromatic amines (HAAs) have received considerable attention in recent years. A major drawback in the analysis of HAAs in foods is their very low level of concentration (0.1 50 ng g-1) as well as matrix interferences. Solid-phase extraction (SPE), forming an integral part of chromatographic analysis, is one of the procedures currently used for the extraction and purification of HAAs in food samples. In this paper a comparative study of several SPE procedures for HAAs determination was performed. Recoveries of the heterocyclic amines in the analysis of both a simple matrix such as a standard methanolic solution and a contaminated meat extract were established. HAAs were determined by HPLC analysis with photodiode-array detection (DAD) of the purified extracts, and the adequacy of different clean-up procedures for the analysis of a contaminated meat extract was discussed.     

Structural characterization and ytterbium spectroscopy in Sc2O3 nanocrystals

Ytterbium-doped scandium oxide nanocrystals measuring less than 25 nm with compositions of Sc_2−xYb_xO₃ (x=0.001-1) were prepared using the modified Pechini method. The Yb:Sc₂O₃ nanocrystals were obtained by calcination at low temperature such as 1073 K for 2 h. X-ray powder diffraction (XRD) and transmission electronic microscopy (TEM) were used to perform the structural characterization of nanocrystals; these studies indicated that the nanocrystals have high crystalline quality with cubic structure and Ia3¯ space group. The morphology and particle size were studied using electron microscopy. A detailed study of the effect of the nanodimension and the ytterbium concentration on the spectroscopic characteristics of Yb³⁺ as an active ion was carried out in terms of optical absorption, optical emission and fluorescence decay time at room and low temperature.     

Determination of 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) in hemoglobin using on-line coupling of restricted access material to liquid chromatography-mass spectrometry

A new method for the analysis of 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) in hemoglobin has been developed. The method is based on a protein hydrolysis with hydrochloric acid to release the bound PhIP followed by purification and preconcentration steps. The sample clean-up consisted of an ultrafiltration of the hydrolyzed protein and preconcentration of PhIP by freeze-drying. An ultimate cleaning step of the sample using restricted access material (RAM) coupled to liquid chromatography performs extraction and enrichment of the analyte from the sample matrix. Three different RAM columns were tested, LiChrospher^®ADS C₄, C₈ and C₁₈. Two mass spectrometers (ion trap and triple quadrupole) operating in different modes were also evaluated for the determination of PhIP released from hemoglobin adducts. Quality parameters were established and good precision (relative standard deviation (R.S.D.) < 15%), suitable accuracy (>95%) and low detection limits were reached, up to 0.03 fmol PhIP/mg hemoglobin, when using the triple quadrupole.