Development and validation of routine analysis methods for the determination of essential, nonessential, and toxic minor and trace elements in cereal and cereal flour samples by inductively coupled plasma-atomic emission spectrometry

Various digestion procedures were carefully investigated and accurately evaluated with respect to their effect on the analysis of cereals and cereal flours. Multielement methods were selected and well developed for the determination of essential (Cr, Cu, Fe, Mg, Mn, and Zn), nonessential (Ag, Al, Ba, Bi, In, and Ga), and toxic (Cd and Pb) minor and trace elements by inductively coupled plasma-atomic emission spectrometry. Only Ag could be determined, either with aqueous standard or standard addition calibration methods, while the standard addition methods were more accurate for the determination of other elements. The recoveries were mostly within the range of 84.1-113% for the expected values of all analytes with respect to certified reference material NIST SRM 1586a (rice flour). The results proved that, for cereals and cereal flours, the use of H2O2 for wet digestion and HNO3 for dry ashing were not necessary. Linear regression analysis and Student's paired t-test were applied to evaluate the significant differences between different procedures and type of samples.     

On-line liquid-liquid extraction system using a new phase separator for flame atomic absorption spectrometric determination of ultra-trace cadmium in natural waters

A robust flow injection (FI) on-line liquid-liquid extraction (LLE) preconcentration/separation system associated with a newly designed gravitational phase separator, coupled to flame atomic absorption spectrometry (FAAS) was developed. The performance of the system was illustrated for cadmium determination at the μg l⁻¹ level. The non-charged cadmium complex with ammonium pyrrolidine dithiocarbamate (APDC) was extracted on-line into isobutyl methyl ketone (IBMK). The organic phase was effectively separated from a large volume of aqueous phase and is led into a 100 μl loop of an injection valve before its introduction into the nebulizer. The system was optimized and offered good performance characteristics with unlimited life time of phase separator, greater flow rate ratios and improved flexibility, as compared with other solvent extraction preconcentration systems. With a sampling frequency of 33 h⁻¹, the enhancement factor was 155, the detection limit was 0.02 μg l⁻¹, the relative standard deviation was 3.2% at 2.0 μg l⁻¹ Cd concentration level and the calibration curve was linear over the concentration range 0.06-6.0 μg l⁻¹. The accuracy of the proposed method was evaluated by analyzing a certified reference material of water and by recovery measurements on spiked samples. Finally, it was successfully applied to the analysis of tapwater, river and seawater samples.     

Determination of arsenic(III) and total inorganic arsenic in water samples using an on-line sequential insertion system and hydride generation atomic absorption spectrometry

A simple and robust on-line sequential insertion system coupled with hydride generation atomic absorption spectrometry (HG-AAS) was developed, for selective As(III) and total inorganic arsenic determination without pre-reduction step. The proposed manifold, which is employing an integrated reaction chamber/gas-liquid separator (RC-GLS), is characterized by the ability of the successful managing of variable sample volumes (up to 25 ml), in order to achieve high sensitivity. Arsine is able to be selectively generated either from inorganic As(III) or from total arsenic, using different concentrations of HCl and NaBH₄ solutions. For 8 ml sample volume consumption, the sampling frequency is 40 h⁻¹. The detection limit is c_L = 0.1 and 0.06 μg l⁻¹ for As(III) and total arsenic, respectively. The precision (relative standard deviation) at 2.0 μg l⁻¹ (n = 10) level is s_r = 2.9 and 3.1% for As(III) and total arsenic, respectively. The performance of the proposed method was evaluated by analyzing the certified reference material NIST CRM 1643d and spiked water samples with various concentration ratios of As(III) to As(V). The method was applied for arsenic speciation in natural waters samples.     

Recent Developments in Flow Injection/Sequential Injection Liquid-Liquid Extraction for Atomic Spectrometric Determination of Metals and Metalloids

Abstract

This review aims to provide a critical overview of automated flow injection and sequential injection liquid-liquid extraction for preconcentration and/or separation of ultra-trace metal and metalloid species hyphenated with atomic spectrometric detection systems, including some new trends and applications in the subbranches of cloud point extraction (CPE), wetting film extraction (WFE), supported liquid membrane extraction (SLME), extraction chromatography (EChr), and liquid-phase microextraction (LPME) techniques. The analytical performance of flow-injection/sequential injection liquid-liquid extraction methods is markedly affected by the components of the flow network such as segmentor, extraction coil, and phase separator. Thus, an overall presentation of system components along with some novel strategies for interface with atomic spectrometers is discussed and exemplified with selected applications.     

On-line liquid phase micro-extraction based on drop-in-plug sequential injection lab-at-valve platform for metal determination

A novel automatic on-line liquid phase micro-extraction method based on drop-in-plug sequential injection lab-at-valve (LAV) platform was proposed for metal preconcentration and determination. A flow-through micro-extraction chamber mounted at the selection valve was adopted without the need of sophisticated lab-on-valve components. Coupled to flame atomic absorption spectrometry (FAAS), the potential of this lab-at-valve scheme is demonstrated for trace lead determination in environmental and biological water samples. A hydrophobic complex of lead with ammonium pyrrolidine dithiocarbamate (APDC) was formed on-line and subsequently extracted into an 80 μL plug of chloroform. The extraction procedure was performed by forming micro-droplets of aqueous phase into the plug of the extractant. All critical parameters that affect the efficiency of the system were studied and optimized. The proposed method offered good performance characteristics and high preconcentration ratios. For 10 mL sample consumption an enhancement factor of 125 was obtained. The detection limit was 1.8 μg L⁻¹ and the precision expressed as relative standard deviation (RSD) at 50.0 μg L⁻¹ of lead was 2.9%. The proposed method was evaluated by analyzing certified reference materials and applied for lead determination in natural waters and urine samples.     

Spectrophotometric Determination of Phenols and Cyanides After Distillation from Natural Waters

Abstract

Total phenols were determined by molecular spectrophotometry, after distillation, complexation with 4-aminoantipyrine and extraction into chloroform. Cyanides were also determined spectrophotometrically after distillation from the acidified samples, and complexation in moderate acidic solution with barbituric acid. The dynamic ranges were 0 – 100 μg L^?1 for total phenols and 0 – 30 μg L^?1 for cyanides. The above methods were applied in the analysis of river, lake and stream waters collected from Northern Greece. The seasonal and spatial variation of concentrations was evaluated by two-way ANOVA. Background levels (4 – 12 μg L^?1 for total phenols and 0.3 – 3 μg L^?1 for cyanides), were found in almost all surface waters, with some exceptions.     

Quantum Boltzmann equations for binary interactions between identical particles

The inhomogeneous master equation obtained in a previous paper (by Van Vliet) is employed to obtain as first-moment equation two quantum mechanical Boltzmann equations (diagonal) for systems of weakly interacting identical particles. The interactions considered are of a binary nature: fermion-fermion or boson-boson. The resulting equations have the same structure as before. The total Boltzmann equation (diagonal and nondiagonal part) is also derived.     

Periodic magnetic modulation of a two-dimensional electron gas: Transport properties

Electrical transport of the two-dimensional electron gas (2DEG) is considered in the presence of a perpendicular magnetic field(B) which is modulated weakly and periodically along one direction by −B₀sin(Kx). The magnetoresistivity exhibits novel oscillations which: 1) are 90° shifted with respect to similar oscillations discovered for a 1D electrical periodic potential, and 2) their amplitude is an order of magnitude larger than for a corresponding electrical potential modulation with strength equal to .