Developing electrodeposition techniques for preconcentration of ultra-traces of Ni, Cr and Pb prior to arc-atomic emission spectrometry determination

Electrodeposition is known to be proper for separation and preconcentration of extremely low concentrations of analytes from the bulk sample which is instrumentally very simple. In the present research, a combination of electrodeposition with arc atomic emission spectrometry (ED-AAES) method has been developed in order to improve the analytical performance of this spectrometry technique. The results show that sensitivity and detection limits by using ED-AAES were improved 1000–2000 folds over those of normal arc atomic emission spectrometry in determination of the selected elements. The detection limits for measurement of Ni, Cr and Pb were 2.56, 3.05 and 2.11 µg L^{− 1} for monodeposition and 3.31, 3.72 and 3.25 µg L^{− 1} for simultaneously deposition, respectively. The precision of determination was in the range of 2–4% RSD. Typical calibration graphs for these elements were linear up to 100 µg L^{− 1}, depending on the element and matrix.Application of this technique was also tested on determination of the studied elements in an electroplating plant's waste water. The accuracy of technique was verified by comparing the results of the waste water analysis with those of electrothermal atomic absorption spectroscopy as a reference standard method.The obtained results show that the combined technique (ED-AAES) has been progressed substantially toward the ultimate goal of direct interference-free determination of trace analysis in complex samples by AAES.     

Cloud point extraction of mercury with PONPE 7.5 prior to its determination in biological samples by ETAAS

Cloud point extraction (CPE) has been used for the pre-concentration of mercury, after the formation of a complex with 2-(5-bromo-2-pyridylazo)-5-(diethylamino)-phenol (5-Br-PADAP), and later analysis by electrothermal atomic absorption spectrometry (ETAAS) using polyethyleneglycolmono-p-nonyphenylether (PONPE 7.5) as surfactant. The chemical variables affecting the separation step were optimized. Under the optimum conditions, i.e, pH 8.5, cloud point temperature 80 degrees C, 5-Br-PADAP=4x10(-5) mol L(-1), PONPE 7.5=0.2%, sample volume=1.0 mL, an enhancement factor of 22-fold was reached. The lower limit of detection (LOD) obtained under the optimal conditions was 0.01 microg L(-1). The precision for 10 replicate determinations at 2.0 microg L(-1) Hg was 4.0% relative standard deviation (R.S.D.). The calibration graph using the pre-concentration system for mercury was linear with a correlation coefficient of 0.9994 at levels near the detection limits up to at least 16 microg L(-1). The method was successfully applied to the determination of mercury in biological samples and in certified reference material (QC METAL LL3).     

A new combined ETAAS method for the determination of platinum, palladium, and gold traces in natural samples

A new combined method is developed for determining trace platinum, palladium, and gold in natural materials of complex composition. The method involves sorption preconcentration with solid-phase extractants obtained by impregnating polymer supports (hypercrosslinked and highly crosslinked polystyrene resins) with an imidazolium ionic liquid (1-hexadecyl-3-methylimidazolium bromide), elution with acetone under normal conditions or with a solution of thiourea in 1 M HCl under microwave heating, and the ETAAS determination of analytes in the eluate. The efficiency of the method is confirmed by the analysis of various ores and rocks.     

Development of a new fluorescence decay measurement system using two-dimensional single-photon counting

A new fluorescence decay measurement system has been developed. The system consists of a spectrograph and a new two-dimensional photon counter. The combination enables measurements to be made of the fluorescence decay as a function of time and wavelength simultaneously. The time resolution is better than 5 ps with deconvolution processing, and the wavelength resolution is approximately 0.15 nm with 1200 grooves mm⁻¹ gratings. The dynamic range is 10⁵. The instrument response function (IRF) of the system is nearly gaussian, and has no tail or “after pulses” which are commonly observed using a photomultiplier in a time-correlated photon counting (TCPC) system. Therefore fast fluorescence decay of several tens of picoseconds can be measured accurately. In addition, the two-dimensional single-photon counting can be performed without wavelength scanning, so that the wavelength-dependent fluorescence decay can be easily and direcly observed with a fast throughput and a high signal-to-noise ratio. The principle of two-dimensional photon counting is discussed together with characteristics including linearity and statistical behavior.     

A new approach for the determination of sulphur in airborne particles by HR-CS ETAAS

In this work, water and nitric acid extractable sulphur concentrations in PM2.5 fraction of urban aerosols were determined by high-resolution continuum source electrothermal molecular absorption spectrometry using most suitable CS molecular absorption band at 258.056 nm. For this purpose, the PM2.5 airborne particulates were collected on quartz filters using a high-volume sampler (500 L/min) in Istanbul (Turkey) during six months (January–June) of two consecutive years. The instrumental and experimental parameters (pyrolysis temperature, molecule formation temperature and leaching reagents) were optimised. The validity of the method for the sulphur was tested using standard reference material and the results were found to be in the uncertainty limits of the certified value.     

A new ion imprinted polymer based on Ru(III)-thiobarbituric acid complex for solid phase extraction of ruthenium(III) prior to its determination by ETAAS

A new ruthenium ion imprinted polymer was prepared from the Ru(III) 2-thiobarbituric acid complex (the template), methacrylic acid or acrylamide (the functional monomers), and ethylene glycol dimethacrylate (the cross-linking agent) using 2,2′-azobisisobutyronitrile as the radical initiator. The ion imprinted polymer was characterized and used as a selective sorbent for the solid phase extraction of Ru(III) ions. The effects of type of functional monomer, sample volume, solution pH and flow rate on the extraction efficiency were studied in the dynamic mode. Ru(III) ion was quantitatively retained on the sorbents in the pH range from 3.5 to 10, and can be eluted with 4 mol L^?1 aqueous ammonia. The affinity of Ru(III) for the ion imprinted polymer based on the acrylamide monomer is weaker than that for the polymer based on the methacrylic acid monomer, which therefore was used in interference studies and in analytical applications. Following extraction of Ru(III) ions with the imprint and their subsequent elution from the polymer with aqueous ammonia, Ru(III) was detected by electrothermal atomic absorption spectrometry with a detection limit of 0.21 ng mL^?1. The method was successfully applied to the determination of trace amounts of Ru(III) in water, waste, road dust and platinum ore (CRM SARM 76) with a reproducibility (expressed as RSD) below 6.4 %.

Development of nanofibrillated cellulose coated with gold nanoparticles for measurement of melamine by SERS

The objective of this study was to develop nanofibrillated cellulose (NFC)-based substrate for rapid detection of melamine in milk by surface-enhanced Raman spectroscopy (SERS). NFC were served as a highly porous platform to load with gold nanoparticles (AuNPs), which can be used as a flexible SERS substrate with nanoscale roughness to generate strong electromagnetic field in SERS measurement. The NFC/AuNP substrate was characterized by UV–Vis spectroscopy and electron microscopy. Milk samples contaminated by different concentrations of melamine were measured by SERS coupled with NFC/AuNP substrate. The spectral data analysis was conducted by multivariate statistical analysis [i.e. partial least squares (PLS)]. Satisfactory PLS result for quantification of melamine in milk was obtained (R = 0.9464). The detection limit for melamine extracted from liquid milk by SERS is 1 ppm, which meets the World Health Organization’s requirement of melamine in liquid milk. These results demonstrate that NFC/AuNP substrate has improved homogeneity and can be used in SERS analysis for food safety applications.     

Evaluation of sulfate-oxalate deposition solution with new electrodeposition system

Journal of Radioanalytical and Nuclear Chemistry - The presented paper defined parameters of electrodeposition and their relationships for selected alpha-emitting radionuclides to be used as an...     

The use of solid-phase extraction and direct injection of a copolymer sorbent as slurry into the graphite furnace prior to determination of cadmium by ETAAS

Abstract

Several aquatic heterogeneous humic-solute fractions with known molecular-size ranges were fractionated further by coupled size-exclusion chromatography (SEC) and polyacrylamide gel electrophoresis (PAGE). The results of SEC-PAGE, obtained for several humic-solute fractions, corresponded reasonably well to the known molecular-size distributions of the dissolved organic matter (DOM). Despite the limited resolving power PAGE appears to offer an alternative coarse method, beside SEC, for fractionation of the heterogeneous humic matter (HM).     

Application of a new ion-imprinted polymer for solid-phase extraction of bismuth from various samples and its determination by ETAAS

A batch process was developed to extract bismuth ions by a novel and selective sorbent. In this study, a new Bi(III)-ion imprinted polymer was prepared by formation of 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol complex for selective preconcentration of ultra trace amounts of bismuth. Polymerization was performed with ethylene glycol dimethacrylate, as crosslinking monomer and methacrylic acid as functional monomer; in the presence of 2,2-azobisisobutyronitrile, as initiator, via bulk polymerization. Optimum pH for maximum sorption was 2.5–3.5. Maximum sorbent capacity and enrichment factor for bismuth were 35.9?mg?g^?1 and 300, respectively. The relative standard deviation and limit of detection the method were evaluated as ±4.1% and 8.6?ng?L^?1. This method is simple, selective and sensitive and can be applied to the determination of bismuth in water, biological and plant samples.     

Utilization of electrodeposition for electrothermal atomic absorption spectrometry determination of gold

Gold was determined by electrothermal atomic absorption spectrometry after electrochemical preconcentration on the graphite ridge probe used as a working electrode and sample support. The probe surface was electrochemically modified with Pd, Re and the mixture of both. The electrolysis of gold was performed under galvanostatic control at 0.5 mA. Maximum pyrolysis temperature for the probe surface modified with Pd was 1200 °C, with Re 1300 °C. The relative standard deviation for the determination of 2 μg l^− 1 Au was not higher than 5.6% (n = 8) for 2 min electrodeposition. The sensitivity of gold determination was reproducible for 300 electrodeposition and atomization cycles. When the probe surface was modified with a mixture of Pd and Re the detection limit was 31 ng l^− 1 for 2 min electrodeposition, 3.7 ng l^− 1 for 30 min, 1.5 ng l^− 1 for 1 h and 0.4 ng l^− 1 for 4 h electrodeposition, respectively. The procedure was applied to the determination of gold in river water samples. The relative standard deviation for the determination of 2.5 ng l^− 1 Au at 4 h electrodeposition time at 0.5 mA was 7.5%.     

Stable free-standing aramid resin film containing vanadium pentoxide and new colour electrochromism of the film by electrodeposition of gold

Vanadium pentoxide (V₂O₅) was electrodeposited on a poly(p-phenylene terephtalamide) (PPTA)-film coated electrode. The cyclic voltammogram of the film had a reversible redox current peak. The film was dark green in the reduced state and yellow in the oxidized state. To obtain new colour, gold was further electrodeposited on the film. Not only the redox current peak but also a new redox current shoulder appeared in the cyclic voltammogram of the obtained film, and it exhibited a multicoloured electrochromism: blackish green ↔ dark green ↔ green ↔  bright red. The red colour in the oxidized state was first obtained for the V₂O₅ film. The new redox current shoulder and the colour were probably due to Au_yV₂O₅ partially formed during electrodeposition of the gold. The redox of the Au_yV₂O₅ was accompanied by egress and ingress of Li⁺ ions and the new colour change.     

Novel unbreakable solid-phase microextraction fiber by electrodeposition of silica sol-gel on gold

A new technique for preparation of an unbreakable solid-phase microextraction (SPME) fiber, using sol-gel technology is developed. Primarily, an ultrathin two-dimensional intermediate film was prepared by hydrolysis of 3-(trimethoxysilyl)-1-propanthiol self-assembled monolayer grafted onto gold, then a stationary phase by electrodeposition of 3-(trimethoxysilyl)propylmethacrylate as a precursor, tetramethyl orthosilicate and polyethylene glycol as a coating polymer was produced. The scanning electron microscopy images revealed that the new fiber exhibits a rather porous and homogenous surface. The thermal stability of the fabricated fiber was investigated by thermogravimetric analysis. The applicability of the prepared fiber coating in conjunction with gas chromatography-mass spectrometry was examined by SPME of polycyclic aromatic hydrocarbons, as model analytes, from aquatic media. An extraction time of 20 min at 50 °C gave maximum peak areas when NaCl, 15% was added to the aqueous samples. Limits of detection were in the range of 0.01-0.02 ng/mL and relative standard deviation values were in the range of 4-16% at 1 ng/mL. The developed method was successfully applied for the analysis of real water samples while the relative recovery percentage was in the range of 102-118%.     

Generation of gold nanostructures at the surface of platinum electrode by electrodeposition for ECL detection for CE

In this paper, we report a sensitive method for ECL detection for CE based on generation of gold nanostructures at the surface of Pt electrode by electrodeposition. Difenidol hydrochloride was used as a model analyte. With the increase of electrodeposition amount, the morphology of gold nanostructures changed from discrete nanoflowers to dense nanoparticle array. Interestingly, the variation of deposition amount also greatly affected the ECL intensity of difenidol. The ECL intensity increased remarkably with deposition amount and reached the maximum value at the deposition amount of 7.0×10^?8C; further increasing the deposition amount, however, caused the ECL intensity to decrease. Other conditions, including applied potential, injection time and voltage, buffer pH, were also optimized in detail. Under the optimized conditions, the linear response range of difenidol is from 1.0×10^?8 to 5.0×10^?5 M, and the detection limit was 4.0×10^?9 M (S/N=3). The RSDs of ECL intensity and migration time were 2.0 and 1.6%, respectively (n=5, at 7.5 μM difenidol). Compared with using bare electrode, the detection sensitivity was significantly improved by ca. two orders of magnitude. Notably, the nanogold was prepared at the surface of electrode and no nanogold was added to the electrophoretic buffer or detection cell, thus causing no interference to the separation. Finally, the proposed method was successfully applied to the analysis of difenidol in tablets and urine samples. With high sensitivity and good reproducibility, this method provides a promising platform for the determination of pharmaceuticals that have a tertiary amine group such as difenidol.     

Impedance sensing of allergen-antibody interaction on glassy carbon electrode modified by gold electrodeposition

The interactions between the recombinant dust mite allergen Der f2 and murine monoclonal antibody were monitored by electrochemical impedance spectroscopy (EIS). Allergen Der f2 were immobilized through the nanogold formed by electrodeposition of gold on planar glassy carbon electrode. A 30-s gold electrodeposition provided a desirable substrate for the immobilization of allergen. Electrochemical deposition of gold on a glassy carbon electrode showed significant improvement in allergen immobilization. The impedance measurements were based on the charge-transfer kinetics of the [Fe(CN)(6)](3-/4-) redox pair. The interactions between allergen and antibody occurred on electrode surface altered the interfacial electron transfer resistance, R(CT), by preventing the redox species approaching the electrode. The results showed that R(CT) increased with increasing concentration of monoclonal antibodies.     

A new geometry for electrodeposition of alpha-emitting nuclides

A new geometry of the alpha-emitting nuclides has been introduced in the electrodeposition system in order to enhance the alpha-spectrum.     

Catalytic deactivation of gold surface as a consequence of Prussian blue electrodeposition and removal

It is shown that the gold surface is catalytically deactivated and smoothened upon removal of the Prussian blue (PB)–gold nanocomposite formed on the gold surface. Atomic force microscopy proves surface smoothening after PB removal. The voltammetric responses of Ru(NH₃)₆Cl₃ on the smoothened surface remain unaffected, but the reactions that involve multistep and inner-sphere electron transfer are affected on the smoothened surface as exemplified by hydroquinone, ferrous oxalate redox reactions, and oxygen reduction. These effects are attributed to catalytic deactivation as a consequence of removal of the active sites.

Simplified cloud point extraction for the preconcentration of ultra-trace amounts of gold prior to determination by electrothermal atomic absorption spectrometry

A simple and sensitive cloud point extraction method has been developed for the preconcentration of ultra-trace amounts of gold as a prior step to its determination by electrothermal atomic absorption spectrometry. It is based on the extraction of gold in hydrochloric acid medium using the non-ionic surfactant polyethyleneglycolmono-p-nonylphenylether (PONPE 7.5) without adding a chelating agent. The preconcentration of a 50 mL sample solution was thus enhanced by a factor of 200. The resulting calibration graph was linear in the range of 10–200 ng L⁻¹ with a correlation coefficient of 0.9993. The limit of detection (3s) obtained under optimal conditions was 2.0 ng L⁻¹. The relative standard deviation for 10 replicate determinations at a 100 ng L⁻¹ Au level was 3.6%. The method was applied to the ultra-trace determination of gold in water and copper samples.