Rapid collection of iron hydroxide for determination of Th isotopes in seawater

This work introduces a novel method of recovery of iron hydroxide using a DIAION CR-20 chelating resin column to determine Th isotopes in seawater with a sector field (SF) inductively coupled plasma mass spectrometer (ICP-MS). Thorium isotopes in seawater were co-precipitated with iron hydroxide, and this precipitate was sent to chelating resin column. Ferric ions in the iron hydroxide were bonded to functional groups of the chelating resin directly, resulting in a pH increase of the effluent by release of hydroxide ion from the iron hydroxide. The co-precipitated thorium isotopes were quantitatively collected within the column, which indicated that thorium was retained on the iron hydroxide remaining on the chelating column. The chelating column quantitatively collected ²³²Th with iron hydroxide in seawater at flow rates of 20–25 mL min⁻¹. Based on this flow rate, a 5 L sample was processed within 3–4 h. The >20 h aging of iron hydroxide tends to reduce the recovery of ²³²Th. The rapid collection method was successfully applied to the determination of ²³⁰Th and ²³²Th in open-ocean seawater samples.     

An off-line automated preconcentration system with ethylenediaminetriacetate chelating resin for the determination of trace metals in seawater by high-resolution inductively coupled plasma mass spectrometry

A novel automated off-line preconcentration system for trace metals (Al, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb) in seawater was developed by improving a commercially available solid-phase extraction system SPE-100 (Hiranuma Sangyo). The utilized chelating resin was NOBIAS Chelate-PA1 (Hitachi High-Technologies) with ethylenediaminetriacetic acid and iminodiacetic acid functional groups. Parts of the 8-way valve made of alumina and zirconia in the original SPE-100 system were replaced with parts made of polychlorotrifluoroethylene in order to reduce contamination of trace metals. The eluent pass was altered for the back flush elution of trace metals. We optimized the cleaning procedures for the chelating resin column and flow lines of the preconcentration system, and developed a preconcentration procedure, which required less labor and led to a superior performance compared to manual preconcentration (Sohrin et al. [5]). The nine trace metals were simultaneously and quantitatively preconcentrated from ∼120 g of seawater, eluted with ∼15 g of 1 M HNO₃, and determined by HR-ICP-MS using the calibration curve method. The single-step preconcentration removed more than 99.998% of Na, K, Mg, Ca, and Sr from seawater. The procedural blanks and detection limits were lower than the lowest concentrations in seawater for Mn, Ni, Cu, and Pb, while they were as low as the lowest concentrations in seawater for Al, Fe, Co, Zn, and Cd. The accuracy and precision of this method were confirmed by the analysis of reference seawater samples (CASS-5, NASS-5, GEOTRACES GS, and GD) and seawater samples for vertical distribution in the western North Pacific Ocean.     

Separation and preconcentration of U(VI) on XAD-4 modified with 8-hydroxy quinoline

Amberlite XAD-4 adsorber resin was modified with 8-hydroxy quinoline (Oxine) by equilibrating with methanol solution of the reagent and the modified resin was used as a support material for the solid phase extraction and preconcentration of UO₂²⁺ from aqueous solution at pH between 4 and 5.5. Ten micrograms of uranium from 300 ml of aqueous phase could be quantitatively extracted in to 1 g of the modified resin giving an enrichment of 200. Uranium collected in the column could be eluted out with methanol-HCl mixture and determined spectrophotometrically using arsenazo(III) as the chromogenic reagent. The preconcentration could be made selective to uranium by using EDTA as a masking agent for transition metal ions and Th(IV).     

A permeation liquid membrane system for determination of nickel in seawater

The use of a permeation liquid membrane system for the preconcentration and separation of nickel in natural and sea waters and subsequent determination by atomic absorption spectroscopy is presented. 2-Hydroxybenzaldehyde N-ethylthiosemi-carbazone (2-HBET) in toluene is used as the active component of the liquid membrane. A study strategy based on a simplex design has been followed. Several chemical and physical parameters were optimized. Maximum permeation coefficient was obtained at a feed solution pH of 9.4, 0.3 mol l⁻¹ of HNO₃ in the stripping solution and 1.66 mmol l⁻¹ of 2-HBTE in toluene as carrier. The precision of the method was 4.7% at 95% significance level and a detection limit of 0.012 μg l⁻¹ of nickel was achieved. The preconcentration procedure showed a linear response within the studied concentration range from 3 to 500 μg l⁻¹ of Ni in the feed solution. The method was validated with different spiked synthetic seawater and certified reference water samples: TMDA-62 and LGC 6016, without matrix interferences and showing good concordance with the certified values, being the relative errors −5.9% and −2.2%, respectively. Under optimal conditions, the average preconcentration yield for real seawater samples was 98 ± 5%, with a nickel preconcentration factor of 20.83 and metal concentrations ranging between 2.8 and 5.4 μg l⁻¹.     

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.     

Chitosan functionalized with di-2-propanolamine: Its application as solid phase extractant for the determination of germanium in water samples by ICP-MS

Cross-linked chitosan was chemically modified with di-2-propanolamine via an arm of chloromethyloxirane (CCTS-DPA resin). The adsorption behavior of the resin towards 62 elements was examined using a mini-column pretreatment method, and the collected elements were eluted with 1 mol L^− 1 nitric acid before measurement by inductively coupled plasma-mass spectrometry (ICP-MS).The CCTS-DPA resin can adsorb several metal cations and several oxoanionic elements at appropriate pH. However, di-2-propanolamine (DPA) attached to cross-linked chitosan (CCTS) showed excellent ability and selectivity for the adsorption of germanium at pH 6 to 9. The adsorption capacity of the resin for germanium (IV) was found to be 106 mg g^− 1 resin, whereas the adsorption rate constant was 9.82 × 10^− 2 min^− 1. Through the column treatment, alkali and alkaline earth matrices in river water and seawater matrices could be completely removed. The resin can also successfully remove chloride and selenium that can interfere with the direct determination of germanium by ICP-MS. The applicability of the CCTS-DPA resin was further demonstrated for the collection/preconcentration of germanium in environmental water samples and its determination by ICP-MS. The concentrations of germanium in tap water, river water and seawater samples were found in the range of 0.011 to 0.022 μg L^− 1.     

Simultaneous preconcentration of uranium(VI) and thorium(IV) from aqueous solutions using a chelating calix[4]arene anchored chloromethylated polystyrene solid phase

A new chelating polymeric sorbent is developed using Merrifield chloromethylated resin anchored with calix[4]arene-o-vanillinsemicarbazone for simultaneous separation and solid phase extractive preconcentration of U(VI) and Th(IV). The “upper-rim” functionalized calix[4]arene-o-vanillinsemicarbazone was covalently linked to Merrifield resin and characterized by FT-IR and elemental analysis. The synthesized chelating polymeric sorbent shows superior binding affinity towards U(VI) and Th(IV) under selective pH conditions. Various physico-chemical parameters that influence the quantitative extraction of metal ions were optimized. The optimum pH range and flow rates for U(VI) and Th(IV) were 6.0-7.0 and 1.0-4.0 ml min⁻¹ and 3.5-4.5 and 1.5-4.0 ml min⁻¹, respectively. The total sorption capacity found for U(VI) and Th(IV) was 48734 and 41175 μg g⁻¹, respectively. Interference studies carried out in the presence of diverse ions and electrolyte species showed quantitative analyte recovery (98-98.5%) with lower limits of detection, 6.14 and 4.29 μg l⁻¹ and high preconcentration factors, 143 and 153 for U(VI) and Th(IV), respectively. The uptake and stripping of these metal ions on the resin were fast, indicating a better accessibility of the metal ions towards the chelating sites. The analytical applicability of the synthesized polymeric sorbent was tested with some synthetic mixtures for the separation of U(VI) and Th(IV) from each other and also from La(III), Cu(II) and Pb(II) by varying the pH and sequential acidic elution. The validity of the proposed method was checked by analyzing these metal ions in natural water samples, monazite sand and standard geological materials.     

Chelating resin from functionalization of chitosan with complexing agent 8-hydroxyquinoline: application for metal ions on line preconcentration system

This study describes the functionalization of biopolymer chitosan, using the complexing agent 8-hydroxyquinoline (oxine) by reaction of diazotization. The chelating resin was characterized by degree of deacetylation, infrared, Raman spectroscopy. The efficiency of the chelating resin and accuracy of the proposed method was evaluated by the metal ion recovery technique in the analysis of potable water, lake water, seawater and a certified sample of oyster tissue. The metal ions Cd(II) and Cu(II) in the samples were previously enriched in a minicolumn and flow injection flame atomic absorption spectrometry (FI-FAAS) determined the concentrations of the analytes. The chelating resin exhibited high selectivity for Cd(II) at pH 7 and for Cu(II) at pH 10. The eluent concentration was tested by the use of HNO₃ in concentrations of 0.1-3 mol l⁻¹ maximum response was obtained at 0.5 mol l⁻¹ for Cd(II) and Cu(II), with R.S.D. values of 0.4%. The analytes gave relative standard deviations (R.S.D.) of 1.5 and 0.7% for solutions of Cd(II) and Cu(II), respectively (n = 7) containing 20 μg l⁻¹ of the metal ions, defining a high reproducibility. The limits of detection (LOD) were 0.1 μg l⁻¹ for Cd(II) and 0.4 μg l⁻¹ for Cu(II). The analytical properties of merit were obtained using the parameters previously optimized with preconcentration time of 90 s. The chelating resin showed chemical stability within a wide range of pH and the efficiency was not altered for the preconcentration of the metal ions during all the experiments.     

Speciation and preconcentration of inorganic antimony in waters by Duolite GT-73 microcolumn and determination by segmented flow injection-hydride generation atomic absorption spectrometry (SFI-HGAAS)

A selective matrix removal/separation/enrichment method, utilizing a microcolumn of a chelating resin with SH functional groups (Duolite GT-73), was proposed for the determination of Sb(III) in waters by segmented flow injection-hydride generation atomic absorption spectrometry (SFI-HGAAS). The resin was selective to Sb(III) at almost all pH and acidity values employed, whereas Sb(V) was not retained at all and could be determined after a pre-reduction step with l-cysteine. Spike recoveries were tested at various concentration levels in different water types and were found to vary between 85 and 118%. Accuracy of the proposed methodology was checked by analyzing a standard reference material and a good correlation was found between the determined (13.3 ± 1.1 μg l⁻¹) and the certified value (13.79 ± 0.42 μg l⁻¹). The method was applied to several bottled drinking water samples for antimony determination with and without preconcentration and none of the samples were found to contain antimony above the permissible level (5 μg l⁻¹). The characteristic concentration (the concentration of the analyte corresponding to an absorbance of 0.0044) was 0.55 μg l⁻¹ and the 3 s limit of detection (LOD) based on five times preconcentration was 0.06 μg l⁻¹. The applicability of the microcolumn separation/preconcentration/matrix removal method for flow injection systems was also demonstrated.     

Determination of REEs in seawater by ICP-MS after on-line preconcentration using a syringe-driven chelating column

A syringe-driven chelating column (SDCC) was applied to develop an on-line preconcentration/inductively coupled plasma mass spectrometry (ICP-MS) method for preconcentration and determination of rare earth elements (REEs) in seawater samples. The present on-line preconcentration system consists of only one pump, two valves, an SDCC, an ICP-MS, several connectors, and Teflon tubes. Optimizations of adsorption pH condition, sample loading flow rate, and integration range were carried out to achieve optimum measurement conditions for REEs in seawater sample. Six minutes was enough for a preconcentration and measurement cycle using 10 mL of seawater sample, where the detection limits for different REEs were in the range of 0.005 pg mL⁻¹ to 0.09 pg mL⁻¹. Analytical results of REEs in a seawater certified reference material (CRM), NASS-5, confirmed the usefulness of the present method. Furthermore, concentrations of REEs in Nikkawa Beach coastal seawater were determined and discussed with shale normalized REE distribution pattern.     

Determination of picomolar beryllium levels in seawater with inductively coupled plasma mass spectrometry following silica-gel preconcentration

A robust and rapid method for the determination of natural levels of beryllium (Be) in seawater was developed to facilitate mapping Be concentrations in the ocean. A solid-phase extraction method using a silica gel column was applied for preconcentration and purification of Be in seawater prior to determination of Be concentrations with inductively coupled plasma mass spectrometry (ICP-MS). Be was quantitatively adsorbed onto silica gel from solutions with pH values ranging from 6.3 to 9, including natural seawater. The chelating agent ethylenediamine tetraacetic acid was used to remove other ions in the seawater matrix (Na, Mg, and Ca) that interfere with the ICP-MS analysis. The reproducibility of the method was 3% based on triplicate analyses of natural seawater samples, and the detection limit was 0.4 pmol kg⁻¹ for 250 mL of seawater, which is sufficient for the analysis of seawater in the open ocean. The method was then used to determine the vertical profile of Be in the eastern North Pacific Ocean, which was found to be a recycled-type profile in which the Be concentration increased with depth from the surface (7.2 pmol kg⁻¹ at <200 m) to deep water (29.2 pmol kg⁻¹ from 3500 m to the bottom).     

A dual column system using agarose-based adsorbents for preconcentration and speciation of chromium in water

Three different agarose-based chelating adsorbents with, respectively, iminodiacetic acid (IDA), tris(2-aminoethyl)amine (TREN) and dipicolylamine (DPA) functional groups and an agarose-based anion exchanger (Q-Sepharose), were studied for the separation and preconcentration of Cr(III) and Cr(VI) species in water. Column recoveries of all the adsorbents were plotted against pH, and it was found that at pH 3.0 the IDA adsorbent selectively adsorbs Cr(III), with a 100 ± 1.0% recovery. The Q-Sepharose, on the other hand, accumulated only Cr(VI) at this pH, again with a recovery of 100 ± 1.0%. A dual column system was accordingly designed, using the two adsorbents in tandem, for the separation and preconcentration of the chromium species.The effects of pH, sample flow rate, column length, eluent type, eluent volume, acid concentration and interfering ions on the recoveries of Cr(III) and Cr(VI) were carefully studied. It was shown that by passing test solutions, at pH 3.0; through the dual column system, the two chromium species could be individually collected on the columns, respectively, and eluted, one after the other. A portion of 2 mol l⁻¹ hydrochloric acid was used for elution of each column before final measurement by flame AAS method. A preconcentration factor of 12, a detection limit of 7.7 ± 0.1 μg l⁻¹ and a precision expressed as relative standard deviation of 0.4% (at 0.3 mg l⁻¹) were achieved for six replicates.Application of the developed method to the determination of chromium species in spiked river and tap water and wastewater samples, from a dye production plant, resulted in excellent agreements with accepted concentrations.     

Simultaneous spectrophotometric determination of trace amounts of uranium, thorium, and zirconium using the partial least squares method after their preconcentration by α-benzoin oxime modified Amberlite XAD-2000 resin

A new solid phase extraction method for separation and preconcentration of trace amounts of uranium, thorium, and zirconium in water samples is proposed. The procedure is based on the adsorption of U(VI), Th(IV) and Zr(IV) ions on a column of Amberlite XAD-2000 resin loaded with α-benzoin oxime prior to their simultaneous spectrophotometric determination with Arsenazo III using orthogonal signal correction partial least squares method. The enrichment factor for preconcentration of uranium, thorium, and zirconium was found to be 100. The detection limits for U(VI), Th(IV) and Zr(IV) were 0.50, 0.54, and 0.48 μg L⁻¹, respectively. The precision of the method, evaluated as the relative standard deviation obtained by analyzing a series of 10 replicates, was below 4% for all elements. The practical applicability of the developed sorbent was examined using synthetic seawater, natural waters and ceramic samples.     

Preconcentration of Zr, Hf, Nb, Ta and W in seawater using solid-phase extraction on TSK-8-hydroxyquinoline resin and determination by inductively coupled plasma-mass spectrometry

Here, we present the first simultaneous preconcentration and determination of ultratrace (pmol kg⁻¹ level) Zr, Hf, Nb, Ta and W in seawater, both in the form of dissolved and acid-dissolvable species. 8-Hydroxyquinoline (8HQ) bonded covalently to a vinyl polymer resin, TSK-8HQ, was used in a chelating adsorbent column to concentrate the metals. The greatest advantage of this resin is its endurance to 5 M HF, since this is an effective eluent for all five metals. The analytes were successfully concentrated from 250 mL seawater with a 50-fold concentration factor through the column extraction and evaporation. The detection limit was 0.009-0.15 pmol kg⁻¹. The procedure blank determined using ultra pure water as a sample was 0.005-0.37 pmol kg⁻¹. The five metals were quantitatively recovered from seawater with good precision (2-4%). The effect of sample pH, sample flow rate, eluent composition and sample pretreatment were carefully studied. This method was applied to seawater.     

Determination of isotopic composition of dissolved copper in seawater by multi-collector inductively coupled plasma mass spectrometry after pre-concentration using an ethylenediaminetriacetic acid chelating resin

Copper is an essential trace metal that shows a vertical recycled-scavenged profile in the ocean. To help elucidate the biogeochemical cycling of Cu in the present and past oceans, it is important to determine the distribution of Cu isotopes in seawater. However, precise isotopic analysis of Cu has been impaired by the low concentrations of Cu as well as co-existing elements that interfere with measurements by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The objective of this study is to develop a simple Cu pre-concentration method using Nobias-chelate PA1 resin (Hitachi High Technologies). This extraction followed by anion exchange, allows precise analysis of the Cu isotopic composition in seawater. Using this method, Cu was quantitatively concentrated from seawater and >99.9999% of the alkali and alkaline earth metals were removed. The technique has a low procedural blank of 0.70 ng for Cu for a 2 L sample and the precision of the Cu isotopic analysis was ±0.07‰ (±2SD, n = 6). We applied this method to seawater reference materials (i.e., CASS-5 and NASS-6) and seawater samples obtained from the northwestern Pacific Ocean. The range of dissolved δ⁶⁵Cu was 0.40–0.68‰.     

Solid phase extraction of copper (II) by sorption on octadecyl silica membrane disk modified with a new Schiff base and determination with atomic absorption spectrometry

A simple, selective and reliable method for rapid extraction and determination of trace amounts of Cu (II) ions from aqueous samples using octadecyl-bonded silica membrane disks modified with bis-(3-methoxy salicylaldehyde)-1,6-diaminohexane and flame atomic absorption spectrometry (FAAS) is presented. Extraction efficiency, the influence of pH, flow rates, amount of ligand, and type and least amount of eluant were investigated. The linear dynamic range of the proposed method for Cu (II) ions was found in a wide concentration range of 1.0 (± 0.2)–150 (± 2) μg l^− 1. The detection limit and preconcentration factor of this method were found 30.0 (± 0.7) ng l^− 1 and 100 respectively. The reproducibility of the procedure is at the most 2.0%. The effects of various cationic interferences on the percent recovery of copper ion were studied. The method was used to the recovery of copper ion from different synthetic, alloys and biological samples.     

Simultaneous spectrophotometric flow-through measurements of pH, carbon dioxide fugacity, and total inorganic carbon in seawater

An autonomous multi-parameter flow-through CO₂ system has been developed to simultaneously measure surface seawater pH, carbon dioxide fugacity (fCO₂), and total dissolved inorganic carbon (DIC). All three measurements are based on spectrophotometric determinations of solution pH at multiple wavelengths using sulfonephthalein indicators. The pH optical cell is machined from a PEEK polymer rod bearing a bore-hole with an optical pathlength of ∼15 cm. The fCO₂ optical cell consists of Teflon AF 2400 (DuPont) capillary tubing sealed within the bore-hole of a PEEK rod. This Teflon AF tubing is filled with a standard indicator solution with a fixed total alkalinity, and forms a liquid core waveguide (LCW). The LCW functions as both a long pathlength (∼15 cm) optical cell and a membrane that equilibrates the internal standard solution with external seawater. fCO₂ is then determined by measuring the pH of the internal solution. DIC is measured by determining the pH of standard internal solutions in equilibrium with seawater that has been acidified to convert all forms of DIC to CO₂. The system runs repetitive measurement cycles with a sampling frequency of ∼7 samples (21 measurements) per hour. The system was used for underway measurements of sea surface pH, fCO₂, and DIC during the CLIVAR/CO₂ A16S cruise in the South Atlantic Ocean in 2005. The field precisions were evaluated to be 0.0008 units for pH, 0.9 μatm for fCO₂, and 2.4 μmol kg⁻¹ for DIC. These field precisions are close to those obtained in the laboratory. Direct comparison of our measurements and measurements obtained using established standard methods revealed that the system achieved field agreements of 0.0012 ± 0.0042 units for pH, 1.0 ± 2.5 μatm for fCO₂, and 2.2 ± 6.0 μmol kg⁻¹ for DIC. This system integrates spectrophotometric measurements of multiple CO₂ parameters into a single package suitable for observations of both seawater and freshwater.     

Determination of Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb in seawater using high resolution magnetic sector inductively coupled mass spectrometry (HR-ICP-MS)

A novel method, combining isotope dilution with standard additions, was developed for the analysis of eight elements (Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb) in seawater. The method requires just 12 mL of sample and employs an off-line pre-concentration step using the commercially available chelating resin Toyopearl AF-Chelate-650M prior to determination by high resolution inductively coupled plasma magnetic sector mass spectrometry (ICP-MS). Acidified samples were spiked with a multi-element standard of six isotopes (⁵⁷Fe, ⁶²Ni, ⁶⁵Cu, ⁶⁸Zn, ¹¹¹Cd and ²⁰⁷Pb) enriched over natural abundance. In addition, standard additions of a mixed Co and Mn standard were performed on sub-sets of the same sample. All samples were irradiated using a low power (119 mW cm⁻²; 254 nm) UV system, to destroy organic ligands, before pre-concentration and extraction from the seawater matrix. Ammonium acetate was used to raise the pH of the 12 mL sub-samples (off-line) to pH 6.4 ± 0.2 prior to loading onto the chelating resin. The extracted metals were eluted using 1.0 M Q-HNO₃ and determined using ICP-MS. The method was verified through the analysis of certified reference material (NASS-5) and the SAFe inter-comparison samples (S1 and D2), the results of which are in good agreement with the certified and reported consensus values. We also present vertical profiles of the eight metals taken from the Bermuda Atlantic Time Series (BATS) station collected during the GEOTRACES inter-comparison cruise in June 2008.     

Synthesis and application of a functionalized resin for flow injection/F AAS copper determination in waters

This paper reports the development of a new strategy for low-level determination of copper in water samples by using a flow-injection system coupled to solid-phase extraction (SPE) using flame atomic absorption spectrometry (F AAS) as detector. In order to preconcentrate copper from samples, a minicolumn packed with a styrene-divinylbenzene resin functionalized with (S)-2-[hydroxy-bis-(4-vinyl-phenyl)-methyl]-pyrrolidine-1-carboxylic acid ethyl ester was used and the synthesis procedure is described. System operation is based on the on-line retention of Cu(II) ions at pH 9.0 ± 0.2 in a such minicolumn with posterior analyte elution with 2 mol l⁻¹ HCl directly to the F AAS nebulizer. The influence of several chemical (sample pH, buffer concentration, HCl eluent concentration and effect of the ionic strength) and flow (sample and eluent flow rates and preconcentration time) variables that could affect the performance of this system were investigated as well as the possible interferents. At optimized conditions, for 2 min of preconcentration time (13.2 ml of sample volume), the system achieved a detection limit of 1.1 μg l⁻¹, a R.S.D. 1% at 20 μg g l⁻¹ and an analytical throughput of 25 h⁻¹, whereas for 4 min of preconcentration time (26.4 ml of sample volume), a detection limit of 0.93 μg l⁻¹, a R.S.D. 5.3% at 5 μg l⁻¹ and a sampling frequency of 13 h⁻¹ were reported.     

An on-line preconcentration/separation system for the determination of bismuth in environmental samples by FAAS

An on-line preconcentration procedure for the determination of bismuth by flame atomic absorption spectrometry (FAAS) has been described. Lewatit TP-207 chelating resin, including iminodiacetate group, packed in a minicolumn was used as adsorbent material. Bi(III) was sorbed on the chelating resin, from which it could be eluted with 3 mol L⁻¹ HNO₃ and then introduced directly to the nebulizer-burner system of FAAS. Best preconcentration conditions were established by testing different resin quantities, acidity of sample, types of eluent, sample and eluent solution volumes, adsorption and elution flow rates, and effect of interfering ions. The detection limit of the method was 2.75 μg L⁻¹ while the relative standard deviation was 3.0% for 0.4 μg mL⁻¹ Bi(III) concentration. The developed method has been applied successfully to the determination of bismuth in pharmaceutical cream, standard reference materials and various natural water samples with satisfactory results.