Determination of trace rare earth elements in environmental samples by low temperature electrothermal vaporization inductively coupled plasma mass spectrometry after synergistic extraction with dimethylheptyl methyl phosphate and 1-phenyl-3-methyl-4-benzoyl-pyrazalone-5.

Synergistic extraction of trace rare earth elements (REEs) from nitrate solutions using mixtures of dimethylheptyl methyl phosphate (P350) and 1-phenyl-3-methyl-4-benzoyl-pyrazalone-5 (PMBP) in hexamethylene has been investigated. The factors affecting the synergistic extraction of rare earth ions, such as pH, organic solvent and phase ratio of organic phase to aqueous phase were systematically studied. The synergistic enhancement factors of P350 and PMBP for REEs were calculated to be 4.3-5.8. After the synergistic extraction, the postextraction organic phase was directly introduced into the graphite furnace for electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) determination. It was found that PMBP along with P350 has an obvious chemical modification for REEs, and the limits of detection (LODs) for 15 REEs were in the range of 0.02-0.09 ng L(-1). The proposed method was found to be more suitable for the analysis of environmental samples with complex matrix.

Determination of trace rare earth elements in coal fly ash and atmospheric particulates by electrothermal vaporization inductively coupled plasma mass spectrometry with slurry sampling.

A method of fluorination assisted electrothermal vaporization (FETV)-ICP-MS with polytetrafluoroethylene as fluorinating reagent was developed for the direct determination of trace rare earth elements (REEs) in coal fly ash and atmospheric particulates. Under the optimal conditions, the detection limits for REEs were 0.1 pg m(-3)(Eu) to 6.7 pg m(-3)(Nd) with the precisions of 4.1%(Yb) to 10%(La) (c=1 microg L(-1), n=9). The proposed method was applied to determine trace REEs in coal fly ash, airborne particulates and NIES SRM No. 8 Vehicle Exhaust Particulates. It was found that the determined values for Y, La, Pr and Nd obtained by slurry sampling FETV-ICP-MS with external calibration coincided with that obtained by pneumatic nebulization (PN)-ICP-MS and slurry sampling FETV-ICP-MS with standard addition. However, the determined values for Ce and Sm obtained by slurry sampling FETV-ICP-MS with external calibration were lower than that obtained by PN-ICP-MS and slurry sampling FETV-ICP-MS with standard addition.

A novel capillary microextraction on ordered mesoporous titania coating combined with electrothermal vaporization inductively coupled plasma mass spectrometry for the determination of V, Cr and Cu in environmental and biological samples.

In this work, an ordered mesoporous titania film was introduced to coat a capillary by means of sol-gel technique. Sol-gel titania coating was developed for the preconcentration/separation of trace V, Cr and Cu by capillary microextraction (CME), and the adsorbed analytes were eluted for electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) detection. By immobilizing sol-gel titania on the inner surface of a fused-silica microextraction capillary, the sol-gel titania coating was prepared easily. Its adsorption properties, stability and the factors affecting the adsorption behaviors of V, Cr and Cu were investigated in detail. At pH range of 7 to 9, the titania-coated capillary (50 cm x 0.25 mm) is selective towards V, Cr and Cu, and the target analytes could be desorbed quantitatively with 50 microl of 1.0 mol l(-1) HNO3 at the rate of 0.05 ml min(-1). With a consumption of 2 ml sample solution, an enrichment factor of 33.3, and a detection limit (3 s) of 1.1 pg ml(-1) (10.5 fg) for V; 3.3 pg ml(-1) (33.0 fg) for Cr and 6.3 pg ml(-1) (63.1 fg) for Cu respectively were obtained. The precisions Relative Standard Deviations (RSDs) for nine replicate measurements of 1 ng ml(-1) V, Cr and Cu were 3.4, 5.1 and 6.4%, respectively. The proposed method has been applied to the determination of V, Cr and Cu in human urine and lake water, and the recoveries for these elements were 89.2 approximately 105%. The developed method was also applied to the determination of the target elements in NIES No. 10-a (rice flour-unpolished) and NIES No. 9 (sargasso) certified reference materials, and the results found are in good agreement with the certified values.

Simultaneous on-line preconcentration and determination of trace metals in environmental samples using a modified nanometer-sized alumina packed micro-column by flow injection combined with ICP-OES.

A novel organic reagent 3-(8-quinolinylazo)-4-hydroxybenzoic acid (QAHBA) was synthesized for chemically modified nanometer-sized alumina, and it was characterized with infrared spectrum and (1)H NMR spectra. By using modified nanometer-sized alumina as micro-column packing material, a new method of flow injection (FI) on-line preconcentration coupled to ICP-OES was developed for simultaneous determination of trace metals (Ag, Pd, Au, Ga, In and Nb) in geological and environmental samples. The effects of pH, sample flow rate, sample volume, elution and interfering ions on the recovery of the analytes have been investigated. Under the optimized operating conditions, the adsorption capacity of the modified nanometer-sized alumina for Ag, Pd, Au, Ga, In and Nb were found to be 5.1, 7.6, 17.7, 15.6, 8.1 and 12.3mgg(-1), respectively. With 4min preconcentration time and 24s elution time, the enrichment factor was 10 and the sample frequency was 10h(-1). The detection limits of this method for Ag, Pd, Au, Ga, In and Nb were 0.12, 0.44, 0.27, 0.19, 0.54 and 0.18mugl(-1), respectively, while the R.S.D.s were 1.6, 2.3, 4.5, 1.6, 1.9 and 1.7% (n=7, c=50ngml(-1)), respectively. The proposed method has been applied to the determination of these trace metals in geological-certified reference materials and natural water samples with satisfactory results.

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 90s and elution time of 18s with enrichment factor of 10 and sampling frequency of 20h(-1) were obtained. The detection limits of this method for the target elements were between 0.03 and 0.36mugL(-1), and the relative standard deviations (R.S.D.s) were found to be less than 6.0% (n=7, c=5ngmL(-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.

Sol-gel zirconia coating capillary microextraction on-line hyphenated with inductively coupled plasma mass spectrometry for the determination of Cr, Cu, Cd and Pb in biological samples.

A sol-gel zirconia coating was developed for the preconcentration/separation of trace Cr, Cu, Cd and Pb by capillary microextraction, and the adsorbed analytes were on-line eluted for detection using inductively coupled plasma mass spectrometry (ICP-MS). By immobilizing sol-gel zirconia on the inner surface of a fused-silica capillary, the sol-gel zirconia coating was simply prepared. Its adsorption properties, stability and the factors affecting the adsorption behaviors of Cr, Cu, Cd and Pb were investigated in detail. In the pH range from 7.8 to 10, the zirconia-coated capillary (35 cm x 0.15 mm) is selective towards Cr, Cu, Cd and Pb, and the analyzed ions could be desorbed quantitatively with 0.2 mL of 0.5 mol/L HNO(3) at a rate of 0.2 mL/min. With a consumption of 1.25 mL sample solution, an enrichment factor of 6.25, and detection limits (3sigma) of 9.9 pg/mL Cr, 17.9 pg/mL Cu, 4.5 pg/mL Cd and 3.7 pg/mL Pb were obtained. The precisions for nine replicate measurements of 1 ng/mL Cr, Cu, Cd and Pb were 4.9% Cr, 2.2% Cu, 2.0% Cd and 3.2% Pb (RSD), respectively. The proposed procedure has been applied to the determination of Cr, Cu, Cd and Pb in human urine, which was subjected to microwave-assisted digestion prior to analysis, and the recoveries for these elements were 89.2-101.8%. In order to validate the developed procedure, a NIES No.10-a Rice Flour-Unpolished certified reference material and a BCR No. 184 Bovine Muscle certified reference material were analyzed, and the results are in good agreement with the certified values.

A comparison of slurry sampling electrothermal vaporization and slurry nebulization inductively coupled plasma mass spectrometry for the direct determination of trace impurities in titanium dioxide powder.

A comparison of slurry sampling (SS)-ETV-ICP-MS and slurry nebulization (SN)-ICP-MS for direct determination of trace impurities in titanium dioxide powder is made. The particle size effect, matrix effect and analytical characteristics of SSETV-ICP-MS and SN-ICP-MS are compared. The results have shown that SSETV-ICP-MS has a lower particle size effect and matrix effect compared to SN-ICP-MS. The analytical performance of the two methods reveals that SSETV-ICP-MS and SN-ICP-MS have similar relative detection limits (in the nanogram per liter level); however, the former has a lower absolute detection limit than the latter. Although the precision for SSETV-ICP-MS is a little worse than that for SN-ICP-MS, it is still acceptable for real sample analysis. The two methods were successfully applied for the determination of trace impurities in titanium dioxide powder samples with particle sizes of less than 50 nm, but only SSETV-ICP-MS could be applied for the determination of trace impurities in titanium dioxide powder samples with a particle size of 1 microm.

Zirconia-coated graphite adsorption bar micro-extraction combined with ETV-ICP-MS for the determination of trace amounts of Cd, Hg and Pb in environmental and biological samples.

In this work, a new and simple micro-extraction method termed graphite adsorption bar micro-extraction was developed, for the first time, for electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) determination of trace Cd, Hg and Pb. In this method, the graphite bar was first coated with zirconia and then inserted into the sample solution for extraction. The graphite bar enriched with the analytes was inserted directly into a graphite tube, and subsequently analyzed by ETV-ICP-MS according to an established temperature program. The experimental parameters, which had influence on the extraction and vaporization, were systematically investigated and the optimal experimental conditions were established. Under the optimized conditions, the detection limits of the method were 0.05, 0.42 and 0.06 pg/ml for Cd, Hg and Pb and the relative standard deviations (RSDs) for 11 replicates at the 0.1 ng/ml level were 7.4, 8.2 and 7.7%, respectively. The proposed method was successfully applied to the determination of trace Cd, Hg and Pb in environmental and biological samples. The results of the experiments indicate that the method has a high enrichment factor and sample utilization efficiency. Furthermore, the method is fast and environment-friendly.

Determination of refractory elements in atmospheric particulates using slurry sampling electrothermal vaporization inductively coupled plasma optical emission spectrometry and inductively coupled plasma mass spectrometry with polyvinylidene fluoride as chemical modifier.

Electrothermal vaporization (ETV) inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS) with polyvinylidene fluoride (PVDF) as chemical modifier are critically compared for the determination of refractory elements in coal fly ash and airborne particulates. The atmospheric particulates that collected on a PVDF filter were introduced into the graphite furnace in the form of a slurry by dissolving the filter in dimethylformamide, and the dissolved filter PVDF, along with additional added PVDF powder, was used as a chemical modifier for subsequent ETV-ICP-OES and ETV-ICP-MS determination. The vaporization behaviors of analytes (Ti, Zr, V, Mo, Cr, La) in ETV-ICP-OES/MS were studied in detail, and the optimal ETV operating parameters were obtained. Under the optimized operating conditions, the detection limits of target elements were 0.08-2.7 ng m(-3) for ETV-ICP-OES and 0.5-50 pg m(-3) for ETV-ICP-MS, respectively, with analytical precisions of 3.5-7.3% for ETV-ICP-OES and 3.9-9.6% for ETV-ICP-MS, respectively. The tolerable amounts of matrix elements for ETV-ICP-OES are higher than for ETV-ICP-MS. Both ETV-ICP-OES and ETV-ICP-MS were used to directly determine the trace refractory elements in coal fly ash and airborne particulates and the analytical results are comparable.

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.

On-line cloud point extraction combined with electrothermal vaporization inductively coupled plasma atomic emission spectrometry for the speciation of inorganic antimony in environmental and biological samples.

A new method for the determination of inorganic Sb species by on-line cloud point extraction combined with electrothermal vaporization inductively coupled plasma atomic emission spectrometry (ETV-ICP-AES) is presented and evaluated. The method is based on the complexation of Sb(III) with pyrrolidine dithiocarbamate (PDC) which form an hydrophobic complex at pH 5.5 and subsequently enter surfactant-rich phase at pH 5.5, whereas Sb(V) remained in aqueous solutions. The preconcentration step is mediated by micelles of the non-ionic surfactant Triton X-114 with ammonium pyrrolidine dithiocarbamate (APDC). The micellar system containing the complex was loaded into the FIA manifold at a flow rate of 2.5 mL min(-1), and the surfactant-rich phase was retained in a microcolumn packed with absorbent cotton, at pH 5.5. After the surfactant-rich phase was eluted with 100 microL acetonitrile, it was determined by ETV-ICP-AES. Sb(V) is reduced to Sb(III) by l-cysteine prior to determined total Sb, and its assay is based on subtracting Sb(III) from total antimony. The main factors affecting separation/preconcentration and the vaporization behavior of analyte in graphite tube were investigated in detail. Under the optimized conditions, the precision relative standard deviation (R.S.D.) for eight replicate measurements of 0.2 microg mL(-1) Sb(III) was 4.3%. The apparent concentration factor, which is defined as the concentration ratio of the analyte in the final diluted surfactant-rich extract ready for ETV-ICP-AES detection and in the initial solution, was 872 for Sb(III). The limit of detection (LOD) for Sb(III) was 0.09 microg L(-1). The proposed method was successfully applied for the speciation of inorganic antimony in different water samples and urine sample with satisfactory results.

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 degrees 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 CHCl(3) 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) (3sigma) 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=0.5mugml(-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.

Optimization of a single-drop microextraction procedure for the determination of organophosphorus pesticides in water and fruit juice with gas chromatography-flame photometric detection.

A single-drop microextraction (SDME) procedure was developed for the analysis of organophosphorus pesticides (OPPs) in water and fruit juice by gas chromatography (GC) with flame photometric detection (GC-FPD). The significant parameters affecting the SDME performance such as selection of microextraction solvent, solvent volume, extraction time, stirring rate, sample pH and temperature, and ionic strength were studied and optimized. Two types of SDME mode, static and cycle-flow SDME, were evaluated. The static SDME procedure provided more sensitive analysis of the target analytes. Therefore, static SDME with tributyl phosphate (TBP) as internal standard was selected for the real sample analysis. The limits of detection (LODs) in water for the six studied compounds were between 0.21 and 0.56ng/mL with the relative standard deviations ranging from 1.7 to 10.0%. Linear response data was obtained in the concentration range of 0.5-50ng/mL (except for dichlorvos 1.0-50ng/mL) with correlation coefficients from 0.9995 to 0.9999. Environmental water sample collected from East Lake and fruit juice samples were successfully analyzed using the proposed method, but none of the analytes in both lake water and fruit juice were detected. The recoveries for the spiked water and juice samples were from 77.7 to 113.6%. Compared with the conventional methods, the proposed method enabled a rapid and simple determination of organophosphorus pesticides in water and fruit juice with minimal solvent consumption and a higher concentration capability.

Microcolumn packed with YPA(4) chelating resin on-line separation/preconcentration combined with graphite furnace atomic absorption spectrometry using Pd as a permanent modifier for the determination of trace mercury in water samples.

A new method using a microcolumn packed with YPA(4) chelating resin as solid-phase extractor has been developed for the separation and preconcentration of trace Hg prior to its measurement by GFAAS with Pd as a permanent modifier. Various parameters such as the amount of the modifier, pH, sample flow rate, the concentration and volume of eluent have been studied in order to find the best conditions for the determination of mercury. The detection limit of the method (3sigma) for Hg based on an enrichment factor of 100 was 0.2ngml(-1). A characteristic mass of 114pg was obtained for mercury using Pd as a permanent modifier. The relative standard deviation was 2.8% at the 10ngml(-1) level (n=5). The method has been applied to the determination of trace mercury in environmental water samples and the recoveries for the spiked samples are in the range of 91-105%.

Determination of trace Cd and Pb in environmental and biological samples by ETV-ICP-MS after single-drop microextraction.

A method based on single-drop microextraction (SDME) combined with electrothermal vaporization (ETV)-ICP-MS was proposed for the determination of trace Cd and Pb. 8-Hydroxyquinoline (8-HQ) was employed as extractant dissolved in several microliters of chloroform and then an organic microdrop was formed at the tip of the microsyringe needle to extract the interest analytes. The vaporization behavior of the metal-8-HQ chelates in graphite furnace was investigated, and the ETV temperature program was optimized. The factors that influenced the extraction efficiency of target analytes (including pH value, flow rate of sample, extraction time and organic microdrop volume) were studied. Under the optimum conditions, the detection limits of the Cd and Pb were 4.6 and 2.9pgmL(-1) with the enrichment factor of 140-fold for Cd and 190-fold for Pb, respectively. The proposed method was applied successfully to the determination of trace Cd and Pb in environmental and biological samples. In order to validate the developed method, a certified reference material of GBW 08501 peach leaves was analyzed and the determined values obtained were in a good agreement with the certified values.

[Study on the adsorption behavior of Ga, In and Tl on nanometer-size titanium dioxide by ICP-AES].

The adsorption behavior of nanometer TiO2 towards Gallium (Ga) Indium (In) and Thallium (Tl) was investigated with inductively coupled plasma atomic emission spectrometry (ICP-AES). The optimum conditions for adsorption were studied in detail, and the test included sorption kinetics, effect of pH on adsorption ratio, enrichment factor, and adsorption capacity. Under the optimum conditions, Ga (III), In(III) and Tl(I) ions could be adsorbed and recovered quantitatively. The static adsorption capacities of Ga(III), In(III) and Tl(I) on nanometer TiO2 were 48.6, 46.6 and 23.4 mg x g(-1) respectively. For the elution of Ga(III), In (III) and Tl(I), a mixture of 0.1 mol x L(-1) EDTA solution and 1.0 mol x L(-1) HNO3 was used, and the recovery ratio was above 92%. According to the definition of IUPAC, the detection limits (3sigma) of this method for Ga, In and Tl with an enrichment factor of 12.5 are 3.0, 6.0 and 13 ng x mL(-1), respectively; and relative standard deviations (RSD) are 1.85%, 1.96% and 3.4%, respectively (n = 6). The proposed method has been applied successfully to the analysis of geological samples with satisfactory results.

Speciation of dissolved iron(II) and iron(III) in environmental water samples by gallic acid-modified nanometer-sized alumina micro-column separation and ICP-MS determination.

A method has been developed for the speciation of trace dissolved Fe(II) and Fe(III) in water by coupling gallic acid (GA) modified nanometer-sized alumina micro-column separation with inductively coupled plasma mass spectrometry (ICP-MS). The separation of Fe(II) and Fe(III) was achieved based on the obvious difference in reaction kinetics between Fe(II) and Fe(III) with GA. Fe(III) was selectively retained on the micro-column at pH 5.5-6.5, while Fe(II) could not be retained by the micro-column at the whole tested pH range of 1.0-6.5, and passed through the micro-column. The Fe(II) can be determined by ICP-MS directly without preconcentration/separation procedure, while Fe(III) retained on the micro-column was then eluted with 1.0 mL of 1 mol L(-1) HCl and determined by ICP-MS. The parameters affecting the separation of Fe(II) and Fe(III) were investigated systematically and the optimum separation conditions were established. Under the optimized conditions, the detection limits of 0.48 microg L(-1) and 0.24 microg L(-1) with relative standard deviation of 5.6% and 4.3%(C= 5 microg L(-1), n= 7) for Fe(II) and Fe(III) were found, respectively. No obvious effect on the speciation of Fe(II) and Fe(III) was found with the change of the ratio of Fe(II) and Fe(III) from 0 ratio 10 to 10 ratio 0. The proposed method was applied for the determination of trace Fe(II) and Fe(III) in environmental water and the recoveries for spiked samples were found to be in the range of 97-105%.

Cloud point extraction for speciation of chromium in water samples by electrothermal atomic absorption spectrometry.

A new method based on the cloud point extraction (CPE) separation and electrothermal atomic absorption spectrometry (ETAAS) detection was proposed for the determination of chromium species. When the system temperature is higher than the cloud point extraction temperature (CPT) of selected surfactant p-octyl polyethyleneglycolphenyether (Triton X-100), the complex of Cr(VI) with dibromophenylfluorone (Br-PF) could enter surfactant-rich phase, whereas the Cr(III) remained in aqueous phase. Thus, an in situ separation of Cr(VI) and Cr(III) could be realized. Cr(VI) in surfactant-rich phase was analyzed by ETAAS and Cr(III) was calculated by subtracting of Cr(VI) from the total chromium which was directly determined by ETAAS. The main factors affecting the cloud point extraction, such as pH, concentration of Br-PF and Triton X-100, equilibration temperature and time, were investigated systematically. Under the optimized conditions, the quantitation limit for Cr(VI) as low as 0.01 microg/L was obtained by preconcentrating a 10 mL sample solution, and the relative standard deviation (n=6, c=2.0 microg/L) was 2.6%. The proposed method was applied to the speciation of chromium in different water samples and the recoveries in the range of 98.9-105.3% were obtained by spiking the real samples. In order to verify the accuracy of the method, a certified reference water sample was analyzed and the results obtained were in good agreement with the certified values.

Speciation of vanadium in water with quinine modified resin micro-column separation/preconcentration and their determination by fluorination assisted electrothermal vaporization (FETV)-inductively coupled plasma optical emission spectrometry (ICP-OES).

A simple and selective method of flow injection (FI) using a micro-column packed with quinine modified resin as solid phase extractant has been developed for preconcentration and separation of trace amount of vanadium(V) and vanadium(IV) in water samples, followed by determination with fluorination assisted electrothermal vaporization (FETV)-inductively coupled plasma optical emission spectrometry (ICP-OES). At pH 3 approximately 3.8, the modified resin is selective towards V(V) and almost not towards V(IV), while, V(IV) could be quantitatively adsorbed by the modified resin at pH 5 approximately 7. The two vanadium species adsorbed by modified resin could be readily desorbed quantitatively with 0.3 ml of 0.5 mol l(-1) HCl. Both vanadium species in elution were then determined by ETV-ICP-OES with the use of polytetrafluoroethylene (PTFE) as chemical modifier. Effects of acidity, sample flow rate, concentration of elution solution and interfering ions on the recovery of the analytes have been systematically investigated. Under the optimal conditions, the adsorption capacities of the quinine modified resin for V(V) and V(IV) are 7.6 and 8.0 mg g(-1), respectively. The detection limit (3sigma) of V is 0.072 ng ml(-1) for FETV-ICP-OES and 0.56 pg ml(-1) for FETV-ICP-MS with enrichment factor of 62.5, and the relative standard deviation (R.S.D.) is 4.9% (n=9, C=0.2 microg ml(-1)) and 3.8% (n=9, C=1.0 ng ml(-1)), respectively. The proposed method has been applied to the determination of trace V(V) and V(IV) in different water samples, and the recoveries of V(V) and V(IV) are 100+/-10%. In order to further verify the accuracy of the developed method, FETV-ICP-MS was employed to analyze the vanadium species in water samples after separation/preconcentration, and analytical results are in good agreement with that obtained by the proposed method. The developed method was also applied to the analysis of the total V in GBW07401 soil certified reference material and in GBW07605 tea leaves certified reference material, and the determined values coincided with the certified values very well.

Speciation of aluminum in drink samples by 8-hydroxyquinoline loaded silylanization silica gel microcolumn separation with off-line ICP-MS detection.

A technique using a flow injection microcolumn separation coupled with ICP-MS detection has been developed for the speciation of Al in drink samples. The retention behaviors of different Al species were studied with 8-hydroxyquinoline (8-HQ) loaded silylanization silica gel as the packing material and inorganic acid (HNO3) as the elution. The results indicated that in a pH range of 5.0 to 8.0, all labile monomeric Al species were retained on the microcolumn while nonlabile monomeric Al species were directly passed through the column. Various Al species after separation were detected by ICP-MS. The detection limit of 0.2 ng mL(-1) and a relative standard deviation (RSD) of 4.2% at 10 ng mL(-1) (n = 11) were achieved, and the recoveries for the spiked samples were 95-108%. The proposed method has been applied to the analysis of Al species in tea infusions, coffee, and tap waters with satisfactory results. The results obtained by this method were compared with that obtained by the cation exchange microcolumn separation and ICP-MS detection system, and some valuable conclusions were drawn.