Application of dispersive liquid-liquid-solidified floating organic drop microextraction and ETAAS for the preconcentration and determination of indium.

A new, simple and efficient method, including dispersive liquid-liquid-solidified floating organic drop microextraction and then electrothermal atomic absorption spectrometry, has been developed for the preconcentration and determination of ultratrace amounts of indium. The method was applied to preconcentrate the indium-1-(2-pyridylazo)-2-naphthol complex in 25 µL 1-undecanol. The various factors affecting the extraction efficiency, such as pH, type and volume of extraction solvent, type and volume of disperser solvent, sample volume, ionic strength, and ligand concentration, were investigated and optimized. Under the optimum conditions, an enrichment factor of 62.5, precision of ±4.75%, a detection limit of 55.6 ng L-1, and for the calibration graph a linear range of 96.0-3360 ng L-1 were obtained. The method was used for the extraction and determination of indium in water and standard samples with satisfactory results. Graphical Abstract Preconcentration of indium ions via liquid-liquid-solidified floating organic drop microextraction method and determination by ETAAS.

Simultaneous column preconcentration of ultra trace amounts of heavy metals with nano-adsorbent in some environmental and biological samples.

In the present investigation, multi-walled carbon nanotubes impregnated by 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane were prepared and applied as adsorbent for the simultaneous separation of Bi(III), Cu(II), Cd(II) and Pb(II) ions prior to their determination by electrothermal atomic absorption spectrometry. The following analytical figures of merit were determined for bismuth, copper, cadmium and lead, respectively: enrichment factors of 168, 134, 111 and 146, assay precisions of ±4.6%, ±4.8%, ±5.3% and ±5.0% and detection limits of 11.3, 3.7, 0.5 and 0.3 ng L(-1). The method was successfully applied for the determination of heavy metals in environmental, biological and certified reference materials.

Column preconcentration and electrothermal atomic absorption spectrometric determination of rhodium in some food and standard samples.

In the present work, an electrothermal atomic absorption spectrometric method has been developed for the determination of ultra-trace amounts of rhodium after adsorption of its 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol/tetraphenylborate ion associated complex at the surface of alumina. Several factors affecting the extraction efficiency such as the pH, type of eluent, sample and eluent flow rates, sorption capacity of alumina and sample volume were investigated and optimized. The relative standard deviation for eight measurements of 0.1 ng/mL of rhodium was ±6.3%. In this method, the detection limit was 0.003 ng/mL in the original solution. The sorption capacity of alumina and the linear range for Rh(III) were evaluated as 0.8 mg/g and 0.015-0.45 ng/mL in the original solution, respectively. The proposed method was successfully applied for the extraction and determination of rhodium content in some food and standard samples with high recovery values.

Synthesis and application of nano-sized ionic imprinted polymer for the selective voltammetric determination of thallium.

A simple and selective thallium imprinted polymer was synthesized as a chemical modifier for the stripping voltammetric determination of Tl ions. The polymerization process (bulk polymerization) was performed with ethylene glycol dimethacrylate (crosslinking monomer) and methacrylic acid (functional monomer) in the presence of 2,2'-azobis(isobutyronitrile) (initiator). The electrochemical method was based on the accumulation of thallium ions at the surface of a modified carbon paste electrode with Tl imprinted polymer and multi-walled carbon nanotubes. After preconcentration process, the voltammetric measurements were carried out via electrolysis of the accumulated Tl ions in a closed circuit. Under the optimized conditions, a linear response range from 3.0 to 240 ng mL(-1) was obtained. The detection limit and RSD (100.0 ng mL(-1) of Tl) were calculated as 0.76 ng mL(-1) and ±2.7%, respectively. The suggested modified electrode has good characteristics such as excellent selectivity, high sensitivity and suitable stability. Also, it was successfully applied for the electrochemical determination of trace amounts of Tl in the environmental and biological samples.

Use of nanoporous Cu(II) ion imprinted polymer as a new sorbent for preconcentration of Cu(II) in water, biological, and agricultural samples and its determination by electrothermal atomic absorption spectrometry.

A new and selective Cu(ll) ion imprinted polymer was prepared by formation of 1-(2-pyridylazo)-2-naphthol complex for selective extraction and preconcentration of Cu ions. Polymerization was performed with ethylene glycol dimethacrylate as a crosslinking monomer and methacrylic acid as a functional monomer in the presence of 2,2'-azobis(isobutyronitrile) as an initiator via a bulk polymerization method. The Cu(ll) imprinted polymeric particles were characterized by scanning electron microscopy and IR spectrometry. The imprint Cu ion was removed from the polymeric matrix using 2 M HNO3. Optimum pH for maximum sorption was 5-8. Maximum sorbent capacity and the enrichment factor for Cu(ll) were 11.3 mg/g and 100, respectively. The RSD and LOD of the method were evaluated as +/-4.3% and 8.7 ng/L, respectively. The proposed method is simple, highly selective, and sensitive and can be applied to the determination of ultratrace amounts of Cu in water, biological, and agricultural samples.

Application of nanoclay for preconcentration of ultra trace amounts of palladium in environmental samples prior to its determination by ETAAS.

In the present work, a batch preconcentration technique using nanoclay with 5-(4-dimethylaminobenzylidene)rhodanine coupled with electrothermal atomic absorption spectrometry was developed for the separation and determination of trace amounts of palladium. In this method, the sample solution was stirred with nanoclay as an adsorbent. Then, adsorbed palladium was subsequently eluted with HCl in acetone (1.5 mol L−1) and, finally, this eluate was injected to electrothermal atomic absorption spectrometry. Under the optimum conditions, the limit of detection and linear dynamic range were found to be 2.6 and 10.0­133 ng L−1 (in original solution), respectively. Furthermore, the enrichment factor and relative standard deviation of seven replicate determinations were 148 and ±5.1 %, respectively. This suggested method is simple, selective and sensitive and can be applied to the extraction and determination of palladium in water, tea leaves, synthetic sample and certified reference material with satisfactory results.

Ligandless, ion pair-based and ultrasound assisted emulsification solidified floating organic drop microextraction for simultaneous preconcentration of ultra-trace amounts of gold and thallium and determination by GFAAS.

In the present work, a new, simple and efficient method for simultaneous preconcentration of ultra-trace amounts of gold and thallium is developed using an ion pair based-ultrasound assisted emulsification-solidified floating organic drop microextraction procedure before graphite furnace atomic absorption spectrometry determination. This methodology was used to preconcentrate the ion pairs formed between AuCl(4)(-) and TlCl(4)(-) and [C(23)H(42)]N(+) in a microliter-range volume of 1-undecanol. Several factors affecting the microextraction efficiency, such as HCl volume, type and volume of extraction solvent, sonication time, sample volume, temperature, ionic strength and [C(23)H(42)]NCl volume were investigated and optimized. Under the optimized conditions, the enrichment factor of 441 and 443 and calibration graphs of 2.2-89 and 22.2-667 ng L(-1) for gold and thallium were obtained, respectively. The intra- and inter-day precision of ± 4.4 and ± 4.9% for Au and ± 4.8 and ± 5.4% for Tl were obtained. The detection limit was 0.66 ng L(-1) for Au and 4.67 ng L(-1) for Tl. The results show that the liquid-liquid pretreatment using ion pair forming, is sensitive, rapid, simple and safe method for the simultaneous preconcentration of gold and thallium. The method was successfully applied for determination of gold and thallium in natural water and hair samples.