Determination of 232Th in seawater by ICP-MS after preconcentration and separation using a chelating resin

This article describes an analytical method for the separation, preconcentration and determination of ²³²Th in seawater samples at sub-ng/L levels using a NOBIAS CHELATE PA1 resin and a sector field (SF) inductively coupled plasma mass spectrometer (ICP-MS). The resin showed excellent adsorption of ²³²Th at a low pH of 2.4 ± 0.4 in a relatively small volume (200 mL) of seawater. ²³²Th adsorbed on the resin was easily eluted using 5 mL of 0.8 M HNO₃. An enrichment factor of 40 was achieved for ²³²Th analysis. Ethylenediamine-tetraacetic acid disodium salt dehydrate (EDTA) was used to investigate the effect of ²³²Th-binding organic ligand on the retention of ²³²Th on the chelating resin. Results obtained using acidified samples (pH of 2.4 ± 0.4) showed EDTA had no significant effect on ²³²Th recovery, indicating that at this low pH, ²³²Th was dissociated from the ²³²Th-binding organic ligand and quantitatively retained on the NOBIAS CHELATE PA1 resin. The developed analytical method was characterized by a separation and preconcentration taking approximately 4 h and a low detection limit of 0.0038 ng/L for ²³²Th, and was successfully applied to the determination of ²³²Th in seawater samples collected from coastal areas, Japan.     

Multielement determination of trace metals in seawater by ICP-MS with aid of down-sized chelating resin-packed minicolumn for preconcentration

The multielement determination of trace metals in seawater was carried out by inductively coupled plasma mass spectrometry (ICP-MS) with aid of a down-sized chelating resin-packed minicolumn for preconcentration. The down-sized chelating resin-packed minicolumn was constructed with two syringe filters (DISMIC 13HP and Millex-LH) and an iminodiacetate chelating resin (Chelex 100, 200-400 mesh), with which trace metals in 50 mL of original seawater sample were concentrated into 0.50 mL of 2 M nitric acid, and then 100-fold preconcentration of trace metals was achieved. Then, 0.50 mL analysis solution was subjected to the multielement determination by ICP-MS equipped with a MicroMist nebulizer for micro-sampling introduction. The preconcentration and elution parameters such as the sample-loading flow rate, the amount of 1 M ammonium acetate for elimination of matrix elements, and the amount of 2 M nitric acid for eluting trace metals were optimized to obtain good recoveries and analytical detection limits for trace metals. The analytical results for V, Mn, Co, Ni, Cu, Zn, Mo, Cd, Pb, and U in three kinds of seawater certified reference materials (CRMs; CASS-3, NASS-4, and NASS-5) agreed well with their certified values. The observed values of rare earth elements (REEs) in the above seawater CRMs were also consistent with the reference values. Therefore, the compiled reference values for the concentrations of REEs in CASS-3, NASS-4, and NASS-5 were proposed based on the observed values and reference data for REEs in these CRMs.     

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.     

Effects of capacity on the preconcentration of trace metals and matrix elimination by an iminodiacetate chelating adsorbent

Low capacity adsorbents, based on iminodiacetic acid and a crosslinked agarose, Novarosetrade mark, have been synthesised for the enrichment of metal ions. Test ions Cu(2+) with high, and Cd(2+) with a moderate affinity for the sorbent were selected. The study includes the effect of specific capacity and matrix composition on the rate of uptake and recovery of these ions. Using a column packed with 0.25 ml of a sorbent and a sample volume of 100 ml, Cu(2+) is quantitatively accumulated from all of the matrices studied even at a capacity of 6 mumol ml(-1) of adsorbent and a flow rate as high as 100 ml min(-1). The enrichment of Cd(2+) is affected by the matrix and for quantitative recovery the flow rate and capacity must be properly adjusted. In the presence of 0.01 M Ca(2+), a specific capacity of 45 mumol ml(-1) is needed for quantitative retainment and a flow rate of 100 ml min(-1), whereas a capacity of 10 mumol ml(-1) suffices at 10 ml min(-1). The advantage of low specific capacity on the removal of matrix elements has been demonstrated. A method based on the determination of conditional stability constants of the metal sorbent complex is suggested for predicting the sorbent capacity needed to acquire quantitative recovery and optimal matrix elimination.     

Neutron activation analysis of some noble metals with preconcentration procedure using a new type of cation chelating resin

The characteristic properties of the chelating resin-3926(II) and the advantage of using it in the preconcentration procedure was described. The chemical recoveries determined by the trace technique were presented. The preconcentration procedure put forward in this paper may be used satisfactorily in neutron activation analysis.     

新型螯合树脂在线预富集测定海水中痕量Cd

将新型螯合树脂(XAD-H2Dz)应用于微柱现场在线采样(MFS)新技术中,实现了海水样中痕量Cd的在线原位预富集和实验室中流动注射-火焰原子吸收(FI-FAAS)系统的联机测定。采样体积为5 mL和50 mL时,检出限(3σ)分别为68和6.7 ng/L;相对标准偏差(n=7)分别为2.0%和2.6%。对国家海水微量元素标准物质GBW(E)080040和实际样品(大连老虎滩区域海水以及连云港黄海水域)中镉进行分析,均获得了满意的结果。     

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.     

Determination of heavy metals and rare earth elements in environmental samples by ICP-MS after solid phase preconcentration with chelating resin fibers and anion exchanger filters.

A solid phase collection/concentration method using anion exchanger filters and a small syringe packed with chelating resin fibers is adopted as a preconcentration tool for trace elements and a separation tool for matrices in aqueous samples prior to the measurement by inductively coupled plasma-mass spectrometry (ICP-MS). The effects of fiber volume, sample volume, eluent volume, and sample flow rate on metal recoveries were investigated in detail to obtain optimum pretreatment conditions. Several heavy metals (HMs) such as, V, Mn, Co, Ni, Cu, Zn, Ga, Cd, Pb, Th and U, as well as 14 rare earth elements (REEs) in sample solutions at pH 6 were quantitatively collected on the solid phase. These adsorbed elements were completely recovered by eluting with 2 ml of 1.0 M nitric acid. At pH 6, more than 99% of alkali and alkaline earth metals in sample solutions were eliminated. The proposed method was evaluated by analyzing two standard reference materials (SRM): peach leaves (NIST 1547) and pond sediment (NIES No. 2). The solid samples were decomposed by microwave-heating and pressurizing acid digestion technique, and then treated by the proposed syringe-type pretreatment method, followed by the ICP-MS measurement. The analytical results for HMs in the SRMs obtained by the present method agreed well with the certified values.     

Trace metals species in sea-water-I: removal of trace metals from sea-water by a chelating resin

A significant fraction of the copper, lead, cadmium and zinc in sea-water exists in a form which is not retained by a chelating resin (Chelex-100) or extracted by ammonium pyrrolidinedithiocarbamate. Anodic stripping voltammetric results suggest that the major part of the unavailable trace metal is adsorbed on, or occluded in, organic or inorganic colloidal particles. An ionic equilibria computer program was used to predict the effect of various complexing agents on trace metal species in sea-water. Citric acid and amino-acids, with the exception of l-cysteine, were shown to be unimportant as complexing agents, and the ability of an EDTA-like ligand to complex Cu, Pb, Cd and Zn is controlled entirely by the concentrations of the ligand and of "labile" Fe(III) and Cr(III) in sea-water, since these two ions together will react quantitatively with EDTA. l-Cysteine, if present in sea-water, would also complex the trace metals.     

Trace ion analysis of seawater by capillary electrophoresis: determination of iodide using transient isotachophoretic preconcentration

An improved transient isotachophoresis (tITP) procedure for the preconcentration of iodide from highly saline matrices was developed with the objective to quantify iodide in seawater by capillary electrophoresis (CE). The procedure takes advantage of introducing cetyltrimethylammonium chloride into the high-sodium chloride background electrolyte, which due to a specific interaction with iodide amended placement of the analyte at a large distance from the matrix chloride (the latter performed the role of a leading anion). Computer simulation showed that 2-(N-morpholino)ethanesulfonate could be adopted as a suitable terminating ion to enable isotachophoretic focusing at the beginning of the CE run. Under optimized tITP conditions, the sensitivity response of iodide was improved by a factor of 140 over normal CE mode. This allowed for direct UV detection of as low as 0.6 microg/L iodide and made feasible CE analysis of undiluted surface seawater samples where iodide was found at a 30 microg/L level. The applicability of the proposed tITP-CE method could apparently be extended to the determination of other trace seawater anions (e.g., iodate).     

Simultaneous multi-element analysis for trace metals in sea water by inductively-coupled plasma/atomic emission spectrometry after batch preconcentration on a chelating resin

Batch treatment with Chelex-100 resin was investigated for preconcentration of trace metals in sea water followed by determination by inductively-coupled plasma atomic emission spectrometry. The preconcentration conditions such as resin weight, stirring time, and amount of ammonium acetate buffer solution were carefully examined for effective multi-element preconcentration from sea water. The resin weight could be decreased to 0.5 g (dry weight) for 1 l of sea water, which was much less than that required in the column method, and a preconcentration factor of 100 was achieved. Al, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Y, Mo, Cd and Pb in sea water were measured with good precision. The detection limits ranged from 6 to 180 ng l^?1. The time required for one sample by the batch method was only 3 h.     

Determination of thorium isotopes in seawater by using preconcentration of thorium-XO complexes on XAD-2 resin

Thorium isotopes in seawater are determined by means of adsorption of the Xylenol Orange /XO: H₆A/ complex onto XAD-2 resin at pH=3 and the XO concentration of 10^–5M, and subsequent purification using an anion-exchange resin, and finally with alpha-spectrometry. The dissolved²³²Th concentration in the western North Pacific surface water is found to range from 0.8 to 1.2 Bq ^–1. The adsorbed species of the Th-XO complex under the experimental conditions has a composition of Th/H₂A/₂ according to the mass balance analysis.     

Trace lead measurement and on-line removal of matrix interference in seawater by isotope dilution coupled with flow injection and ICP-MS

Isotope dilution analysis method coupled with flow injection and inductively coupled plasma mass spectrometry (ID-FI-ICP-MS), enabled trace lead concentration in seawater to be determined and the high salt concentration in the matrix, such as Na⁺, Ca²⁺ and Mg²⁺, to be removed on-line. The operational parameters of the FI system including pH for the chelating reaction, concentration of 8-hydroxyquinoline-5-sulfonic acid (8-HQS), sample loading time and injection speed, washing time and speed, eluting acid concentration and eluting speed, and instrumental parameters for ICP-MS were optimized and selected. Accurate results could be achieved because the isotope ratios required can be precisely measured in the range of the eluting peak by means of ID-FI-ICP-MS. The 3σ detection limit was 0.204 ng ml⁻¹. The trace lead concentration of seawater in south Xiamen, China was 0.988 ± 0.039 ng ml⁻¹. The recoveries of spiked Pb standard in seawater and standard reference water (GBW 08607) were 97.9 and 101.0%, respectively, with a relative standard deviation of 0.98%. This method can be used to determine trace lead concentration in high salt matrix samples, and is especially useful when the eluting peaks do not have a Gaussian-distribution.     

Radionuclide X-ray fluorescence analysis of drinking water using preconcentration of trace metals on chelating cellulose exchanger OSTSORB-OXIN

Determination of Cr, Fe, Cu, Zn and Pb in drinking water preconcentrated on a chelating ion exchanger of Czechoslovak production is described. The analytical system consisted of a radionuclide source²³⁸Pu, a Si/Li semiconductor detector and a multichannel analyzer. Results are compared with trehshold limit values recommended for drinking water.     

Determination of uranium in seawater by flow-injection preconcentration on dodecylamidoxime-impregnated resin and spectrophotometric detection

A flow injection method has been developed for the determination of uranium in seawater combining the on-line preconcentration with spectrophotometric detection. An aliquot (10 mL) of the seawater sample adjusted to pH 5.5 was injected into the analytical system and uranium was adsorbed on the column packed with styrene-divinylbenzene copolymer resin (Bio-Beads SM-2) modified with dodecylamidoxime which showed high selectivity to uranium. Uranium was then eluted with 0.01 M hydrochloric acid and detected spectrophotometrically after the reaction with Chlorophosphonazo III. Interference from calcium and strontium was masked with cyclohexanediaminetetraacetic acid added to the chromogenic reagent solution. The sample throughput, the detection limit (3σ), and the preconcentration factor were 23 per hour, 0.13 μg/L, and 20, respectively, when the sample injection volume was kept at 10 mL. The precision at the 2 μg/L level was less than 4% (RSD). The proposed method was applied to the determination of uranium in the seawater samples collected off the Boso peninsula, Japan and the uranium concentration was found to be ca. 3 μg/L, which is close to the literature data. The yield of the recovery test ranged from 95% to 99%.     

Shipboard analysis of picomolar levels of manganese in seawater by chelating resin concentration and chemiluminescence detection

A new shipboard analytical method for determining picomolar levels of manganese in seawater has been developed. The method is based on a combination of chelating resin column extraction and improved chemiluminescence (CL) detection in a closed flow system. In this method, manganese in sample solution is selectively collected on newly-developed iminodiacetate-immobilized chelating resin, and then eluted with acidic solution containing hydrogen peroxide. The resulting eluent is mixed with luminol solution and aqueous ammonia after removal of iron ions by a chelating resin column, and then the mixture is introduced into the CL cell. The manganese concentration is obtained from the CL intensity. The detection limit (3SD) of manganese is 5 pmol L^–1 from 9 mL of seawater sample. The method was applied to seawater samples collected at the Okinawa Trough.     

Separation preconcentration method for platinum and rhodium from environmental samples using a chelating resin

A method of determining trace levels of platinum and rhodium in different samples was investigated. The method involves separation and preconcentration of the platinum and rhodium from the matrix by flow injection (FI) on-line coupled with electrothermal atomic absorption spectrometry (ETAAS) with Zeeman effect background correction. Platinum and rhodium were adsorbed on a microcolumn packed with 1,5-bis(di-2-pyridyl)methylene thiocarbohydrazide immobilized on silica gel (DPTH-gel). The sorbed metals were directly eluted with nitric acid into the graphite furnace and determined by AAS.     

Speciation of chromium in seawater by ICP-AES with dual mini-columns containing chelating resin.

A method for the preconcentration and speciation of chromium in seawater was developed. On-line preconcentration and determination were carried out by using inductively coupled plasma atomic emission spectrometry (ICP-AES) with dual mini-columns containing a chelating resin. In this system, Cr(III) was collected on the first column. The effluent containing residual chromium from the first column was collected on the second column after passing through a reduction-switching unit, in which the reducing agent was introduced, or not, for the reduction of Cr(VI) to Cr(lII). Cr(VI) was determined as the difference between the concentration of pre-reduced Cr(VI) and Cr(III) in the effluent from the first column. The detection limits for Cr(III) and Cr(VI) were 0.04 and 0.09 microg l(-1), respectively.     

Speciation of inorganic tellurium from seawater by ICP-MS following magnetic SPE separation and preconcentration

A new method was developed for the speciation of inorganic tellurium species in seawater by inductively coupled plasma-MS (ICP-MS) following selective magnetic SPE (MSPE) separation. Within the pH range of 2-9, tellurite (Te(IV)) could be quantitatively adsorbed on gamma-mercaptopropyltrimethoxysilane (gamma-MPTMS) modified silica-coated magnetic nanoparticles (MNPs), while the tellurate (Te(VI)) was not retained and remained in solution. Without filtration or centrifugation, these tellurite-loaded MNPs could be separated easily from the aqueous solution by simply applying external magnetic field. The Te(IV) adsorbed on the MNPs could be recovered quantitatively using a solution containing 2 mol/L HCl and 0.03 mol/L K2Cr2O7. Te(VI) was reduced to Te(IV) by L-cysteine prior to the determination of total tellurium, and its assay was based on subtracting Te(IV) from total tellurium. The parameters affecting the separation were investigated systematically and the optimal separation conditions were established. Under the optimal conditions, the LOD obtained for Te(IV) was 0.079 ng/L, while the precision was 7.0% (C = 10 ng/L, n = 7). The proposed method was successfully applied to the speciation of inorganic tellurium in seawater.