Matrix separation of palladium and iridium by the cellulose anion exchanger Cellex T and the subsequent determination of palladium at theμg/g-level

The preconcentration and separation of palladium and iridium from base metals is studied with cellulose (Cellex T) and styrene-divinylbenzene (Varion AT 400) anion exchangers. In spite of lower capacity of Cellex T to chloride complexes of Pd and Ir, it allowed to get a higher preconcentration factor. Yields of 92–99% are achieved for Pd and 96–97% for Ir from the solutions containing great excess of base and heavy metals. Graphite furnace atomic absorption spectrometry is used for the final measurements. The procedure has been applied to the determination of palladium in natural samples.     

Preconcentration of copper with multi-walled carbon nanotubes pretreated by potassium permanganate cartridge for solid phase extraction prior to flame atomic absorption spectrometry

A procedure for the preconcentration of copper was described in this paper using multi-walled carbon nanotubes (MWCNTs) oxidized by potassium permanganate as the adsorbent for the enrichment of trace copper in water samples. Important parameters, such as the sample pH, the concentration and volume of eluent, sample flow rate and volume, and interference of coexisting ions, were investigated. The obtained results indicated that proposed method possessed an excellent analytical performance. The linear range, the detection limit, and precison (RSD) were 1-100 ng/mL (R2 = 0.9993), 0.32 ng/mL and 2.88%, respectively. The results showed that copper could be adsorbed quantitatively on the pretreated MWCNTs with potassium permanganate, and proposed method was very useful in the monitoring of copper in the environment.     

Evaluation of digestion procedures for the determination of iron and zinc in biscuits by flame atomic absorption spectrometry

An evaluation is made of different digestion methods for the determination of iron and zinc in biscuits prior to flame atomic absorption analysis. For the initial studies, microwave digestion was enough (using hydrogen chloride and nitric acid 3:1, v/v, at 180 °C and 600 W) to provide comparable accuracy, precision, digestion time and non-critical handling of reagents to dry-ashing and wet digestion (using different acid mixtures) and also to a simple acid treatment at room temperature. Although, after a simple microwave digestion, the spiked recoveries were found around 96–102%, to reduce the digestion time and for simplicity we worked on wet acid treatments. The results showed that acid-only treatment is not enough to digest the samples without adding ethanol, which was found necessary to digest organic residue at room temperature. The method was validated by comparison of the data found for commercial biscuit samples through using the proposed procedure and the AOAC official reference spectrophotometric method. Fe concentration in the different biscuits (such as petit beurre, baby biscuits, etc.) ranged from 1.21 to 15.96 mg/100 g while Zn concentration ranged from 0.58 to 2.50 mg/100 g depending on biscuit type. The highest concentration of Fe was in baby biscuits and these biscuits were about thirteen times richer in Fe than petit beurre biscuits.     

Use of modified rice husks as a natural solid adsorbent of trace metals: characterisation and development of an on-line preconcentration system for cadmium and lead determination by FAAS

The use of rice husks as an alternative adsorbent in an on-line preconcentration system for Cd (II) and Pb (II) determination by flame atomic absorption spectrometry (FAAS) is described. The potential of rice husks as a natural adsorbent was evaluated as a material modified with 0.75 mol l⁻¹ NaOH solution and in the unmodified form. For this task, several techniques such as spectroscopy and thermogravimetry were used for elucidation of possible functional groups responsible for the uptake of Cd (II) and Pb (II). Furthermore, based on adsorption studies and adsorption isotherms applied to the Langmüir model, it was possible to verify that modified rice husks present a higher adsorption capacity for both metals. After establishing this material as a promising natural adsorbent, it was used for on-line preconcentration of Cd (II) and Pb (II) metals. The multivariate optimisation of chemical and flow variables was performed by using a full factorial design (2⁴) including the following factors: preconcentration time, preconcentration flow rate, concentration and volume of eluent. The optimum pH values used for on-line preconcentration were taken from prior univariate experiments. Under optimised conditions for Cd (II) determination (4 min of preconcentration at a 6 ml min⁻¹ preconcentration flow rate, in which comprises 24 ml of preconcentration volume, 200 μl elution volume and 1.0 mol l⁻¹ HNO₃ solution as eluent), the system achieved a detection limit of 1.14 μg l⁻¹ and an enrichment factor of 72.4. Similar conditions were used for Pb (II) determination (4 min of preconcentration, 6 ml min⁻¹ preconcentration flow rate, 300 μl elution volume and 1.0 mol l⁻¹ HNO₃ solution as eluent) from which a detection limit of 14.1 μg l⁻¹ and enrichment factor of 46.0 were achieved. Also, rice husks have been shown to be a homogeneous and stable adsorbent in which more than 100 preconcentration/elution cycles provide a relative standard deviation (RSD) of less than 6.0% on the analytical signal. The satisfactory accuracy of the method developed was obtained by using spiked water samples (mineral water and lake water) and spiked red wine samples. These values were confirmed by electrothermal atomic absorption spectrometry (ETAAS). The certified reference material [pig kidney (CRM 186)] and the reference material [beech leaves (CRM 100)] were also used.     

分析信号处理方法的比较研究

研究了高效液相色谱－火焰原子吸收光谱联用系统分析信号处理方法，比较了各种处理方法的优缺点，用积分与适应平滑法综合处理色谱峰分析信号，不仅能有效地消除噪声，而且能使分析信号得到加强，以测定镍为例，经积分与适应平滑法综合处理后，检出限改善了２．７倍。     

Trends in Preconcentration Procedures for Metal Determination Using Atomic Spectrometry Techniques

 Methods for metal preconcentration are often described in the literature. However, purposes are often different, depending on whether the methods are applied in environmental, clinical or technological fields. The respective method needs to be efficient, give high sensitivity, and ideally also is selective which is useful when used in combination with atomic spectroscopy. This review presents the actual tendencies in metal preconcentration using techniques such as Flame Atomic Absorption Spectrometry (FAAS), Electrothermal Atomic Absorption Spectrometry (ETAAS), Hydride Generation Atomic Absorption Spectrometry (HGAAS), Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Procedures based on related to electrochemical, coprecipitation/precipitation, liquid–liquid and solid–liquid extraction and atom trapping mechanisms are presented. Correspondence: Department of Analytical Chemistry, Universidade Estadual de Campinas – UNICAMP, P.O. Box 6154, 13083-970 Campinas, Brazil. e-mail: zezzi@iqm.unicamp.br Received December 20, 2001; accepted October 11, 2002     

Probing in vitro digestion at oil–water interfaces

Interfacial layers have been widely applied to study the formation and stability of emulsion-based systems. However, the application of isolated interfaces to address digestibility of emulsions is often limited because of the complexity of experimental methods and results. This review summarizes the latest developments in analytical methods and literature data on effects of digestion on interfacial layers. Particular emphasis is given to understand the changes on interfacial magnitudes during oral, gastric, and duodenal digestion, either applied separately or sequentially. Limitations of interfacial aspects and key factors that influence emulsion microstructure in bulk and lipid digestion are identified. Understanding the behavior of interfacial layers upon gastrointestinal digestion promotes an accurate tracking of the physiological fate of emulsions.     

几种杂多阴离子柱撑水滑石的合成与吸附行为

柱撑水滑石类层柱状阴离子粘土是一类新型层柱材料，由于其二维孔道结构的可调变性及潜在的择形催化性能，已引起人们的重视[1-3]．迄今，人们已合成了包括无机和有机阴离子，同多和杂多阴离子（Polyoxometalates，简称POMs）以及配合物阴离子在内的多种柱撑水滑石，其中同多和     

Geometries,vibrational frequencies,and electron affinities of X2Cl (X=C,Si,Ge) clusters

Ab initio quantum chemical calculations have been performed on X₂Cl^? and X₂Cl (X = C, Si, Ge) clusters. The geometrical structures, vibrational frequencies, electronic properties and dissociation energies are investigated at the Hartree–Fock (HF), Møller–Plesset second‐ and fourth‐order (MP2, MP4), CCSD(T) level with the 6‐311+G(d) basis set. The X₂Cl (X = C, Si, Ge) and X₂Cl^? (X = Si, Ge) take a bent shape obtained at the ground state, while C₂Cl^? has a linear structure. The impact on internal electron transfer between the X₂Cl and the corresponding anional clusters is studied. The three different types of electron affinities (EAs) at the CCSD(T) are reported. The most reliable adiabatic electronic affinities, obtained at the CCSD(T)/cc‐pvqz level of theory, are predicted to be 3.30, 2.62, and 1.98 eV for C₂Cl, Si₂Cl, and Ge₂Cl, respectively. The calculated EAs of C₂Cl and Ge₂Cl are in good agreement with theoretical results reported. The correlation effects and basis sets effects on the geometrical structures and dissociation energies are discussed. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Direct determination of manganese in vitamin-mineral tablets using solid sampling electrothermal atomic absorption spectrometry

Manganese in vitamin-minerals tablets was determined by solid sampling electrothermal atomic absorption spectrometry (SS-ETAAS) using three different calibration methods, namely calibration against aqueous standards, standard addition with aqueous standards on solid samples and calibration against solid certified standards. Samples were only finely ground and introduced directly into the furnace by means of solid autosampler system without any dissolving process. Effects of different calibration techniques, temperatures and heating rates of atomization and pyrolysis steps on the accuracy and precision of the analyte elements were investigated. After optimization of the experimental parameters, there is good agreement (at 95% confidence level) between the results obtained by solid sampling and those obtained by acid digestion of samples.