Solid phase extraction of metal ions using carbon nanotubes

The sorption behaviour of carbon nanotubes (CNTs) toward some divalent metal ions such as Cu(II), Co(II), Ni(II), Zn(II), Pb(II), Mn(II) and Cd(II) has been investigated systematically. The affinity order of the metal ions towards CNTs at pH in the range of 7.0-9.0 was: Cu(II) > Pb(II) > Zn(II) > Co(II) > Ni(II) > Cd(II) > Mn(II). The experimental parameters for preconcentration of copper, which exhibits the highest affinity towards carbon nanotubes, on a microcolumn packed with CNTs prior to its determination by flame atomic absorption spectrometry have been investigated. Copper can be quantitatively retained at pH 8.2 from sample volume up to 150 mL and then eluted completely with 0.1 mol L^− 1 HNO₃. The limit of detection limit for Cu(II) determination with FAAS detection was 2.1 μg L^− 1, and the RSD was 3.5% at the 50 μg L^− 1 level. Under the optimal conditions for copper enrichment also Zn(II), Pb(II) and Ni(II) could be quantitatively preconcentrated from water samples. The method was validated using a certified reference materials BCR-610 and SRM 1640.     

Carbon Nanofibers as Solid‐Phase Extraction Adsorbent for the Preconcentration of Trace Rare Earth Elements and Their Determination by Inductively Coupled Plasma Mass Spectrometry

Abstract

Systematic investigations were carried out into the sorption of rare earth elements (REEs) on carbon nonofibers (CNFs) by inductively coupled plasma mass spectrometry (ICP‐MS). The experimental parameters for preconcentration of REEs, such as pH, sample flow rate and volume, eluent concentration, and interfering ions on preconcentration of REEs have been examined in detail. The studied metal ions can be adsorbed quantitatively on CNFs in a pH range from 2.0 to 5.0, and then eluted completely with 0.5 mol l^?1 HNO₃. Based on the above facts, a novel method using a microcolumn packed with carbon nanofibers as an adsorption material was developed for the separation and preconcentration of REEs prior to their determination by ICP‐MS. The proposed method has been successfully applied to the determination of light (La), medium (Eu and Gd) and heavy (Yb) rare earth elements in real sample with the recovery more than 90%. In order to validate this method, two certified reference materials of tea leaves (GBW 07605) and mussel (GBW 08571) were analyzed, and the determined values are in good agreement with the certified values.     

Mesoporous titanium dioxide as a novel solid-phase extraction material for flow injection micro-column preconcentration on-line coupled with ICP-OES determination of trace metals in environmental samples

Mesoporous titanium dioxide as a novel solid-phase extraction material for flow injection micro-column preconcentration on-line coupled with ICP-OES determination of trace metals (Co, Cd, Cr, Cu, Mn, Ni, V, Ce, Dy, Eu, La and Yb) in environmental samples was described. Possessing a high adsorption capacity towards the metal ions, mesoporous titanium dioxide has found to be of great potential as an adsorbent for the preconcentration of trace metal ions in samples with complicated matrix. The experimental parameters including pH, sample flow rate, volume, elution and interfering ions on the recovery of the target analytes were investigated, and the optimal experimental conditions were established. Under the optimized operating conditions, a preconcentration time of 90 s and elution time of 18 s with enrichment factor of 10 and sampling frequency of 20 h⁻¹ were obtained. The detection limits of this method for the target elements were between 0.03 and 0.36 μg L⁻¹, and the relative standard deviations (R.S.D.s) were found to be less than 6.0% (n =7, c =5 ng mL⁻¹). The proposed method was validated using a certified reference material, and has been successfully applied for the determination of the afore mentioned trace metals in natural water samples and coal fly ash with satisfactory results.     

Multiwalled carbon nanotubes microcolumn preconcentration and determination of gold in geological and water samples by flame atomic absorption spectrometry

The potential of multiwalled carbon nanotubes (MWNTs) as solid-phase extraction adsorbent for the separation and preconcentration of gold has been investigated. Gold could be adsorbed quantitatively on MWNTs in the pH range of 1–6, and then eluted completely with 2 mL of 3% thiourea in 1 mol L^− 1 HCl solution at a flow rate of 0.5 mL min^− 1. A new method using a microcolumn packed with MWNTs as sorbent has been developed for the preconcentration of trace amount of Au prior to its determination by flame atomic absorption spectrometry. Parameters influencing the preconcentration of Au, such as pH of the sample, sample flow rate and volume, elution solution and interfering ions, have been examined and optimized. Under the optimum experimental conditions, the detection limit of this method for Au was 0.15 µg L^− 1 with an enrichment factor of 75, and the relative standard deviation (R.S.D) was 3.1% at the 100 µg L^− 1 Au level. The method has been applied for the determination of trace amount of Au in geological and water samples with satisfactory results.     

Further study on a flow injection on-line multiplexed sorption preconcentration coupled with flame atomic absorption spectrometry for trace element determination

A further study on a newly developed flow injection (FI) on-line multiplexed sorption preconcentration (MSP) using a knotted reactor coupled with flame atomic absorption spectrometry (FAAS) was carried out to demonstrate its applicability and limitation for trace element determination. For this purpose, Cr(VI), Cu(II), Ni(II) and Co(II) were selected as the analytes, and detailed comparison was made between the MSP-FAAS and conventional FI on-line sorption preconcentration FAAS in respect to retention efficiency and linear ranges of absorbance versus sample loading flow rate and total preconcentration time. Introduction of an air-flow for removal of the residual solution in the KR after each sub-injection in the MSP procedure played a decisive role in the improvement of retention efficiency. The linearity of absorbance versus sample loading flow rate or total preconcentration time was extended to a more degree for the metal ions with less stability of their PDC (pyrrolidine dithiocarbamate) complexes than those with more stable PDC complexes. It seems that the MSP procedure behaves advantages beyond the inflection points in the diagrams of absorbance versus total preconcentration time and sample loading flow rate obtained by conventional (a single continuous) preconcentration procedure. With a sample loading flow rate of 6.0 ml min⁻¹ and a total preconcentration time of 180 s, the retention efficiencies were increased from 25, 46, 41 and 63% with a single continuous sorption preconcentration to 44, 78, 65 and 75% with a six sub-injection preconcentration procedure for Cr(VI), Co(II), Ni(II), and Cu(II), respectively. The detection limits were 0.40, 0.33, 0.31 and 0.26 μg l⁻¹ for Cr(VI), Co(II), Ni(II), and Cu(II), respectively. The precision (R.S.D.) for eleven replicate determination of 2 μg l⁻¹ Cr(VI), Co(II) and Ni(II), and 1 μg l⁻¹ Cu(II), was 2.1, 4.1, 2.6 and 1.7%, respectively.     

Volatilization of Cr, Co, Mn and Ni as their pyrrolidinecarbodithioate chelates from electrothermal vaporizer for sample introduction in inductively coupled plasma optical emission spectrometry

Based on gaseous compound introduction as pyrrolidinecarbodithioate chelates of Cr, Co, Mn and Ni by electrothermal vaporization (ETV) in inductively coupled plasma optical emission spectrometry (ICP-OES), a novel method for the determination of trace Cr, Co, Mn and Ni was developed. It was found that in the presence of ammonium pyrrolidinecarbodithioate (APDC) the trace amounts of analytes were vaporized at a low temperature of 1500 °C. The main factors affecting the formation and vaporization of analytes chelates were investigated in detail. Thermal gravimetric analysis of Cr-APDC, Co-APDC, Mn-APDC and Ni-APDC chelates and UV-vis analysis of the sample vapor collected in CHCl₃ after vaporization of their chelates indicated that the analytes were vaporized and transported into ICP as their chelates. Under the optimized conditions, the limits of detection (LOD) (3σ) and the relative standard deviations (R.S.D.) of Cr, Co, Mn and Ni were 0.36, 0.19, 0.073 and 0.32 ng, and 3.9, 4.9, 3.8 and 3.3% (c = 0.5 μg ml⁻¹, n = 7), respectively. By combination with a solvent extraction step, the proposed method had been successfully applied to analysis of Cr, Co, Mn and Ni in the artificial seawater. To evaluate the accuracy of the developed method, two certified reference materials (human hair GBW 09101 and poplar leaves GBW 07604) were also analyzed, and the determined values obtained were in good agreement with the certified values.     

Preconcentration and determination of trace elements with 2-aminoacetylthiophenol functionalized Amberlite XAD-2 by inductively coupled plasma-atomic emission spectrometry

2-Aminoacetylthiophenol (AATP)-modified Amberlite XAD-2 has been synthesized by coupling it through NNNH group. The resulting chelating resin, characterized by elemental analysis, thermogravimetric analysis (TGA) and infrared (IR) spectra, was used to preconcentrate Cd, Hg, Ag, Ni, Co, Cu and Zn ions. Several parameters, such as distribution coefficient and sorption capacity of the chelating resin, pH and flow rates of uptake and striping, volume of sample and eluent, were evaluated. The effects of electrolytes and cations on the preconcentration were also investigated. The recoveries were >96%. The procedure was validated by standard addition and analysis of a standard reference sediment material (GBW 07309 China). The developed method was utilized for preconcentration and determination of Cd, Hg, Ag, Ni, Co, Cu and Zn in tap water, river water and sediment samples by inductively coupled plasma-atomic emission spectrometry (ICP-AES) with satisfactory results. The 3σ detection limits for Cd, Hg, Ag, Ni, Co, Cu and Zn were found to be 0.10, 0.23, 0.41, 0.13, 0.25, 0.39 and 0.58 μg l⁻¹, respectively. The relative standard deviation of the determination was <10%.     

Preconcentration of trace metals with 2-(methylthio)aniline-functionalized XAD-2 and their determination by flame atomic absorption spectrometry

2-(Methylthio)aniline-modified Amberlite XAD-2 has been synthesized by coupling it through a NNNH group. The resulting chelating resin, characterized by elemental analysis, thermogravimetric analysis and infrared spectra, was used to preconcentrate Cd, Hg, Ni, Co, Cu and Zn ions. Several parameters, such as the distribution coefficient and sorption capacity of the chelating resin, pH and flow rates of uptake and stripping, and volume of sample and eluent, were evaluated. The effect of electrolytes and cations on the preconcentration was also investigated. The recoveries were >96%. The procedure was validated by standard addition and analysis of a standard river sediment material (GBW 08301, China). The developed method was utilized for preconcentration and determination of Cd, Hg, Ni, Co, Cu and Zn in tap water and river water samples by flame atomic absorption spectrometry with satisfactory results. The 3σ detection limit and 10σ quantification limit for Cd, Hg, Ni, Co, Cu and Zn were found to be 0.022, 0.028, 0.033, 0.045, 0.041, 0.064 μg l⁻¹ and 0.041, 0.043, 0.052, 0.064, 0.058, 0.083 μg l⁻¹, respectively.     

The use of Agrobacterium tumefacients immobilized on Amberlite XAD-4 as a new biosorbent for the column preconcentration of iron(III), cobalt(II), manganese(II) and chromium(III)

A microorganism Agrobacterium tumefacients as an immobilized cell on a solid support was presented as a new biosorbent for the enrichment of Fe(III), Co(II), Mn(II) and Cr(III) prior to flame atomic absorption spectrometric analysis. Amberlite XAD-4 was used as a support material for column preconcentration. Various parameters such as pH, amount of adsorbent, eluent type and volume, flow rate of sample solution, volume of sample solution and matrix interference effect on the retention of the metal ions have been studied. The optimum pH for the sorption of above mentioned metal ions were about 6, 8, 8 and 6, respectively. The loading capacity of adsorbent for Co(II) and Mn(II) were found to be 29 and 22 μmol g⁻¹, respectively. The recoveries of Fe(III), Co(II), Mn(II) and Cr(III), under the optimum conditions were found to be 99 ± 3, 99 ± 2, 98 ± 3 and 98 ± 3%, respectively, at the 95% confidence level. The limit of detection was 3.6, 3.0, 2.8 and 3.6 ng ml⁻¹ for Fe(III), Co(II), Mn(II) and Cr (III), respectively, by applying a preconcentration factor of 25. The proposed enrichment method was applied for metal ion determination from water samples, alloy samples, infant foods and certified samples such as whey powder (IAEA-155) and aluminum alloy (NBS SRM 85b). The analytes were determined with a relative error lower than 10% in all samples.     

Solid phase extractive preconcentration of trace metals using p-tert-butylcalix[4]arene-1,2-crown-4-anchored chloromethylated polymeric resin beads

5,11,17,23-Tetrakis(1,1-dimethylethyl)-25,26-dihydroxy-27,28-crown-4-calix[4]arene in the cone conformation was synthesized. This p-tert-butylcalix[4]arene-1,2-crown-4 compound was then anchored with Merrifield chloromethylated resin beads. The modified polymeric resin was characterized by ¹H NMR, FT-IR and elemental analysis and used successfully for the separation and preconcentration of Cu(II), Cd(II), Co(II), Ni(II) and Zn(II) prior to their determination by FAAS. Effective extraction conditions were optimized in both batch and column methods. The resin exhibits good separating ability with maximum between pH 6.0-7.0 for Cu(II), pH 6.0 for Cd(II), pH 5.0 for Co(II), pH 4.0-4.5 for Ni(II), and pH 4.5 for Zn(II). The elution studies were carried out with 0.5 mol L⁻¹ HCl for Cu(II), Co(II) and Co(II), 1.0 mol L⁻¹ HCl for Cd(II) and Zn(II). The sorption capacity, preconcentration factor and distribution coefficient of each metal ion were determined. The detection limits were 1.10, 1.25, 1.83, 1.68 and 2.01 μg L⁻¹ for Cu(II), Cd(II), Co(II), Ni(II) and Zn(II). The influence of several ions on the resin performance was also investigated. The validity of the proposed method was checked for these metal ions in NIST standard reference material 2709 (San Joaquin Soil) and 2711 (Montana Soil).     

Automatic on line preconcentration and determination of lead in water by ICP-AES using a TS-microcolumn

A simple, sensitive, low-cost and rapid, flow injection system for the on-line preconcentration of lead by sorption on a microcolumn packed with silica gel funtionalized with methylthiosalicylate (TS-gel) was developped. The metal is directly retained on the sorbent column and subsequently then eluted from it by EDTA. Five variables (sample flow rate, eluent flow rate, eluent concentration, pH and buffer concentration) were considered as factors in the optimization process. Interactions between analytical factors and their optimal levels were investigated using two level factorial and Box-Behnken designs. The optimum conditions established were applied to the determination of lead by flow injection inductively coupled plasma atomic emission spectrometry (FI-ICP-AES). The proposed method has a linear calibration range from 10 to at least 500 ng ml⁻¹ of lead. At a sample frequency of 24 h⁻¹ and a 120 s preconcentration time, the enrichment factor was 41, the detection limit was 15.3 ng ml⁻¹ (S/N=3) and the precision, expressed as relative standard deviation, was 0.9% (at 100 ng ml⁻¹). Validation of the developed method was carried out against electrothermal atomic absorption spectrometry analysis without statistically significant differences between the proposed method and the atomic absorption method.     

2-{[1-(3,4-Dihydroxyphenyl)methylidene]amino}benzoic acid immobilized Amberlite XAD-16 as metal extractant

2-{[1-(3,4-Dihydroxyphenyl)methylidene]amino}benzoic acid (DMABA) was loaded on Amberlite XAD-16 (AXAD-16) via azo linker and the resulting resin AXAD-16-DMABA explored for enrichment of Zn(II), Mn(II), Ni(II), Pb(II), Cd(II), Cu(II), Fe(III) and Co(II). The optimum pH values for extraction are 6.5-7.0, 5.0-6.0, 5.5-7.5, 5.0-6.5, 6.5-8.0, 5.5-7.0, 4.0-5.0 and 6.0-7.0, respectively. The sorption capacity was found between 97 and 515 μmol g⁻¹ and the preconcentration factors from 100 to 450. Tolerance limits for foreign species are reported. The kinetics of sorption is fast as t_1/2 is ≤5 min. The chelating resin can be reused for 50 cycles of sorption-desorption without any significant change (<1.5%) in the sorption capacity. The limit of detection values (blank +3 s) are 1.12, 1.38, 1.76, 0.67, 0.77, 2.52, 5.92 and 1.08 μg L⁻¹ for Zn(II), Mn(II), Ni(II), Pb(II), Cd(II), Cu(II), Fe(III) and Co(II), respectively. The enrichment on AXAD-16-DMABA coupled with monitoring by flame atomic absorption spectrometry (FAAS) is used to determine all the metal ion ions in river and synthetic water samples, Co in vitamin tablets and Zn in milk samples.     

Nanometer-sized zirconium dioxide microcolumn separation/preconcentration of trace metals and their determination by ICP-OES in environmental and biological samples

A new method is proposed using a microcolumn (20 mm × 2.0 mm) packed with nanometer-sized zirconia as solid-phase extractor for the separation/preconcentration of Mn, Cu, Cr, Zn, Ni and Co prior to their determination by inductively coupled plasma optical emission spectrometer (ICP-OES) in environmental samples. The factors affecting the separation and preconcentration of analytes such as pH, sample flow rate and volume, eluent concentration and volume were determined, interfering ions were studied, and the optimal experimental conditions were established. The adsorption capacity of nanometer-sized ZrO₂ for Mn, Cu, Cr, Zn, Ni and Co was found to be 1.3, 1.3, 1.7, 2.0, 3.9 and 1.5 mg g⁻¹, respectively. The detection limits of the method were 12, 58, 24, 2, 7 and 36 ng L⁻¹, respectively, with a preconcentration factor of 25. The precision of this method was 1.7% (Mn), 2.9% (Cu), 5.9% (Mn), 3.8% (Mn), 6.2% (Mn) and 4.3% (Mn) with 9 determinations of 10 ng mL⁻¹ of target analytes, respectively. The method was successfully applied to the determination of trace metals in lake water, dried fish samples, certified reference materials of human hair and milk, and provided satisfactory results.     

On-line preconcentration and separation of Co, Ni and Cd via capillary microextraction on ordered mesoporous alumina coating and determination by inductively plasma mass spectrometry (ICP-MS)

In this paper, an ordered mesoporous alumina coating was prepared and applied to capillary microextraction (CME) of trace Co, Ni and Cd for the first time. The coated capillary was used for on-line coupling CME with inductively plasma mass spectrometry (ICP-MS) for the determination of trace metals of Co, Ni and Cd. The porous structure of Al₂O₃ coating was examined by SEM and TEM. The effects of the extraction parameters including pH, sample flow rate and volume, elution solution and interfering ions on the recovery of analytes have been investigated and optimized. Under the optimized conditions, the limits of detection were 0.33, 1.5 and 1.4 ng L⁻¹ for Co, Ni and Cd, respectively, with a preconcentration factor of 10 times. The precisions for all investigated elements were 2.7, 4.1 and 2.5% (c = 0.05 ng L⁻¹, n = 7), for Co, Ni and Cd, respectively, and the sample frequency was 8 h⁻¹.The proposed method was successfully applied for the analysis of trace metals in water, rice and urine samples with the recovery of 94-105%. In order to validate the proposed method, two certified reference materials of GBW 0913 human urine and NIES No.10-b rice flour were analyzed, and the determination values are in good agreement with the certified values. The ordered mesoporous Al₂O₃ coated capillary can be used more than 20 times without decreasing the extraction efficiency.     

Column solid-phase extraction with Chromosorb-102 resin and determination of trace elements in water and sediment samples by flame atomic absorption spectrometry

A column, solid-phase extraction (SPE), preconcentration method was developed for determination of Bi, Cd, Co, Cu, Fe, Ni and Pb ions in drinking water, sea water and sediment samples by flame atomic absorption spectrometry. The procedure is based on retention of analytes in the form of pyrrolidine dithiocarbamate complexes on a short column of Chromosorb-102 resin from buffered sample solution and then their elution from the resin column with acetone. Several parameters, such as pH of the sample solution, amount of Chromosorb-102 resin, amount of ligand, volume of sample and eluent, type of eluent, flow rates of sample and eluent, governing the efficiency and throughput of the method were evaluated. The effects of divers ions on the preconcentration were also investigated. The recoveries were >95%. The developed method was applied to the determination of trace metal ions in drinking water, sea water and sediment samples, with satisfactory results. The 3σ detection limits for Cd, Cu, Fe, Ni and Pb and were found to be as 0.10, 0.44, 11, 3.6, and 10 μg l⁻¹, respectively. The relative standard deviation of the determination was <10%. The procedure was validated by the analysis of a standard reference material sediment (GBW 07309) and by use of a method based on coprecipitation.     

A solid phase extraction using a chelate resin immobilizing carboxymethylated pentaethylenehexamine for separation and preconcentration of trace elements in water samples

A chelate resin immobilizing carboxymethylated pentaethylenehexamine (CM-PEHA resin) was prepared, and the potential for the separation and preconcentration of trace elements in water samples was evaluated through the adsorption/elution test for 62 elements. The CM-PEHA resin could quantitatively recover various elements, including Ag, Cd, Co, Cu, Fe, Ni, Pb, Ti, U, and Zn, and rare earth elements over a wide pH range, and also Mn at pH above 5 and V and Mo at pH below 7. This resin could also effectively remove major elements, such as alkali and alkaline earth elements, under acidic and neutral conditions. Solid phase extraction using the CM-PEHA resin was applicable to the determination of 10 trace elements, Cd, Co, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn, in certified reference materials (EnviroMAT EU-L-1 wastewater and ES-L-1 ground water) and treated wastewater and all elements except for Mn in surface seawater using inductively coupled plasma atomic emission spectrometry. The detection limits, defined as 3 times the standard deviation for the procedural blank using 500 mL of purified water (50-fold preconcentration, n = 8), ranged from 0.003 μg L⁻¹ (Mn) to 0.28 μg L⁻¹ (Zn) as the concentration in 500 mL of solution.     

Speciation analysis of inorganic arsenic in natural water by carbon nanofibers separation and inductively coupled plasma mass spectrometry determination

In this paper, carbon nanofibers (CNFs) as a novel solid phase extraction sorbent were developed for speciation preconcentration and separation of inorganic arsenic species As(III) and As(V) prior to determination by inductively coupled plasma mass spectrometry (ICP-MS). It was found that during all the steps of the separation, As(III) was selectively sorbed on the microcolumn packed with CNFs within a pH range of 1.0-3.0 in the presence of ammonium pyrroinedithiocarbamate (APDC), while As(V) was passed through the microcolumn without the retention. Various experimental parameters affecting the separation and determination of As(III) and As(V) have been investigated in detail. Under the optimized conditions, the detection limits of this method for As(III) were 0.0045 ng mL⁻¹ with an enrichment factor of 33 and 0.24 ng mL⁻¹ for As(V), and the relative standard deviations for As(III) and As(V) were 2.6% and 1.9% (n = 9, c = 1.0 ng mL⁻¹), respectively. In order to verify the accuracy of the method, a certified reference of water sample was analyzed, and the results obtained were in good agreement with the certified values. The proposed method was applied for the analysis of inorganic arsenic species in groundwater and lake water with the recovery of 92-106%.     

The uses of 1-(2-pyridylazo) 2-naphtol (PAN) impregnated Ambersorb 563 resin on the solid phase extraction of traces heavy metal ions and their determinations by atomic absorption spectrometry

1-(2-pyridylazo) 2-naphtol (PAN) impregnated Ambersorb 563 resin was used as solid phase extractor of copper, nickel, cadmium, lead, chromium and cobalt ions in aqueous solutions prior to their atomic absorption spectrometric determinations. The parameters including pH, sample volume, matrix effects were also investigated. The relative standard deviation (R.S.D.) of the combined method of sample treatment, preconcentration and determination with atomic absorption spectrometry is generally lower than 10%. The limit of detection was between 0.21 and 1.4 μg l⁻¹. The results were used for preconcentration of analyte ions from natural water samples. The method was also applied to a stream sediment standard reference material (GBW7309) for the determination of Cu, Ni, Cd, Pb, Cr and Co.     

Nanometer titanium dioxide immobilized on silica gel as sorbent for preconcentration of metal ions prior to their determination by inductively coupled plasma atomic emission spectrometry

Nanometer titanium dioxide immobilized on silica gel (immobilized nanometer TiO₂) was prepared by sol-gel method and characterized by using X-ray diffraction (XRD) and scanning electron microscope (SEM). The adsorptive potential of immobilized nanometer TiO₂ for the preconcentration of trace Cd, Cr, Cu and Mn was assessed in this work. The metal ions studied can be quantitative retained at a pH range of 8-9, and 0.5 mol L⁻¹ HNO₃ was sufficient for complete elution. The adsorption capacity of immobilized nanometer TiO₂ for Cd, Cr, Cu and Mn was found to be 2.93, 2.11, 6.69 and 2.47 mg g⁻¹, respectively. A new method using a microcolumn packed with immobilized nanometer TiO₂ as sorbent has been developed for the preconcentration of trace amounts of Cd, Cr, Cu and Mn prior to their determination by inductively coupled plasma atomic emission spectrometry (ICP-AES). The method has been successfully applied for the determination of trace elements in some environmental samples with satisfactory results.     

Synthesis of amidinothioureido-silica gel and its application to flame atomic absorption spectrometric determination of silver, gold and palladium with on-line preconcentration and separation

A simple and highly selective flow injection (FI) on-line preconcentration and separation flame atomic absorption spectrometric (FAAS) method was developed for the determinations of trace amounts of silver, gold and palladium. The selective preconcentration of the noble metals was achieved in a wide range of sample acidity (0.1-6 M HNO₃ or HCl) on a microcolumn packed with amidinothioureido-silica gel (ATuSG). The analytes retained on the column were effectively eluted with 5.0% thiourea solution. The analytical procedure was optimized for sample acidity, elution, interferences, flow rate of sampling and eluting, and concentration of sample. Common co-existing cations and anions did not interfere with the preconcentration and determination of the three metals. At a sample loading flow rate of 4.5 ml min⁻¹ with 60 s preconcentration, detection limits (3σ) of 1.1 ng ml⁻¹ Ag, 13 ng ml⁻¹ Au and 17 ng ml⁻¹ Pd were obtained. The precisions (R.S.D., n=11) were 1.2% for Ag, 1.2% for Au and 1.7% for Pd, respectively. The detection limits can be further improved by increasing sample volume. The analytical results obtained by the proposed method for a number of standard reference materials were in good agreement with the certified values.