Simultaneous extraction and preconcentration of uranium and thorium in aqueous samples by new modified mesoporous silica prior to inductively coupled plasma optical emission spectrometry determination

A new synthesized modified mesoporous silica (MCM-41) using 5-nitro-2-furaldehyde (fural) was applied as an effective sorbent for the solid phase extraction of uranium(VI) and thorium(IV) ions from aqueous solution for the measurement by inductively coupled plasma optical emission spectrometry (ICP OES). The influences of some analytical parameters on the quantitative recoveries of the analyte ions were investigated in batch method. Under optimal conditions, the analyte ions were sorbed by the sorbent at pH 5.5 and then eluted with 1.0 mL of 1.0 mol L⁻¹ HNO₃. The preconcentration factor was 100 for a 100 mL sample volume. The limits of detection (LOD) obtained for uranium(VI) and thorium(IV) were 0.3 μg L⁻¹. The maximum sorption capacity of the modified MCM-41 was found to be 47 and 49 mg g⁻¹ for uranium(VI) and thorium(IV), respectively. The sorbent exhibited good stability, reusability, high adsorption capacity and fast rate of equilibrium for sorption/desorption of uranium and thorium ions. The applicability of the synthesized sorbent was examined using CRM and real water samples.     

Analysis of nickel-niobium alloys by inductively coupled plasma optical emission spectrometry

Inductively coupled plasma optical emission spectrometry (ICP-OES) was applied to the analysis of major and minor elements of Ni-Nb alloys obtained by aluminothermic reduction process. Digestion of samples was made using a mixture of HF+HNO₃. Minor and trace elements were determined without matrix separation. The precision for all constituents was <3%. Recoveries for the analyte-spiked samples were 95%.     

电感耦合等离子体-发射光谱分析中硫酸基体效应及抑制

研究了电感耦合等离子体-发射光谱分析中的硫酸基体效应及克服干扰的有效方法。对2%~20%范围内4种不同体积分数H2SO4溶液中30种元素的基体效应进行了观察,发现H2SO4对各元素的谱线发射强度均存在明显的抑制作用。实验证实体积分数5%乙酸可有效抑制H2SO4的基体效应,并建立了H2SO4溶液中痕量元素的电感耦合等离子体-发射光谱分析法。     

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).     

Determination of impurities in magnesium niobate by slurry introduction axially viewed inductively coupled plasma optical emission spectrometry

A simple preparation scheme is described for the quantitative analysis of a magnesium niobate sample using slurry introduction axially viewed inductively coupled plasma optical emission spectrometry. Relationships between the stability of slurries and the conditions, such as particle size, pH, dispersant and amount of dispersant, were investigated experimentally. The MgNb₂O₆ slurry sample was prepared by adding the dispersant sodium polyacrylate and agitation in an ultrasonic bath to ensure good dispersion. Under optimization of pH and amount of dispersant, an analysis of minor and trace impurities (Ba, Ca, Cr, Cu, Fe, Mn, Ni, Pb) in magnesium niobate was accomplished. Applying a paired t test, we showed that the results were in agreement at a 95% confidence level with the reference values obtained by a fusion method for a magnesium niobate sample, which verified that the calibration curves could be established by aqueous standards. Analytical results demonstrate that the factors that affected the accuracy of determination for MgNb₂O₆ are mainly the particle size of the sample and the stability of slurry.     

Carbon-related matrix effects in inductively coupled plasma atomic emission spectrometry

In Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES), it has been observed that the emission intensity of some atomic lines is enhanced or depressed by the presence of carbon in the matrix. The goal of this work was to investigate the origin and magnitude of the carbon-related matrix effects in ICP-AES. To this end, the influence of the carbon concentration and source (i.e. glycerol, citric acid and potassium hydrogen phthalate), the experimental conditions and sample introduction system on the aerosol characteristics and transport, plasma excitation conditions and the emission intensity of several atomic and ionic lines of a total of 15 elements has been studied. Results indicate that carbon related matrix effects do not depend on the carbon source and they become more severe when the amount of carbon loaded into the plasma increases, i.e., when using: (i) carbon concentrations higher than 5 g L^− 1; (ii) high sample uptake rates; and (iii) efficient sample introduction systems. Thus, when introducing carbon into the plasma, the emission intensity of atomic lines with excitation energies below 6 eV is depressed (up to 15%) whereas the emission intensity of atomic lines of higher excitation energies (i.e. As and Se) are enhanced (up to 30%). The emission intensity of the ionic lines is not affected by the presence of carbon. The origin of the carbon-related interferences on the emission intensity of atomic lines is related to changes in the line excitation mechanism since the carbon containing solutions show the same aerosol characteristics and transport efficiencies as the corresponding aqueous solutions. Based on the previous findings, a calibration approach for the accurate determination of Se in a Se-enriched yeast certified material (SELM-1) has been proposed.     

Direct determination of impurities in high purity silicon carbide by inductively coupled plasma optical emission spectrometry using slurry nebulization technique

A novel method for the determination of Al, Ca, Cr, Cu, Fe, Mg, Mn, Ni and Ti in high purity silicon carbide (SiC) using slurry introduction axial viewed inductively coupled plasma optical emission spectrometry (ICP-OES) was described. The various sizes of SiC slurry were dispersed by adding dispersant polyethylene imine (PEI). The stability of slurry was characterized by zeta potential measurement, SEM observation and signal stability testing. The optimal concentration of PEI was found to be 0.5 wt% for the SiC slurry. Analytical results of sub-μm size SiC by the slurry introduction were in good accordance with those by the alkaline fusion method which verified that determination could be calibrated by aqueous standards. For μm size SiC, results of most elements have a negative deviation and should be calibrated by the Certified Reference Material slurry. Owing to a rather low contamination in the sample preparation and stability of the slurry, the limits of detection (LODs), which are in the range of 40-2000 ng g⁻¹, superior to those of the conventional nebulization technique by ICP-OES or ICP-MS.     

Method development for the determination of manganese, cobalt and copper in green coffee comparing direct solid sampling electrothermal atomic absorption spectrometry and inductively coupled plasma optical emission spectrometry

A method has been developed for the determination of cobalt, copper and manganese in green coffee using direct solid sampling electrothermal atomic absorption spectrometry (SS-ET AAS). The motivation for the study was that only a few elements might be suitable to determine the origin of green coffee so that the multi-element techniques usually applied for this purpose might not be necessary. The three elements have been chosen as test elements as they were found to be significant in previous investigations. A number of botanical certified reference materials (CRM) and pre-analyzed samples of green coffee have been used for method validation, and inductively coupled plasma optical emission spectrometry (ICP OES) after microwave-assisted acid digestion of the samples as reference method. Calibration against aqueous standards could be used for the determination of Mn and Co by SS-ET AAS, but calibration against solid CRM was necessary for the determination of Cu. No significant difference was found between the results obtained with the proposed method and certified or independently determined values. The limits of detection for Mn, Cu and Co were 0.012, 0.006 and 0.004 μg g⁻¹ using SS-ET AAS and 0.015, 0.13 and 0.10 μg g⁻¹ using ICP OES. Seven samples of Brazilian green coffee have been analyzed, and there was no significant difference between the values obtained with SS-ET AAS and ICP OES for Mn and Cu. ICP OES could not be used as a reference method for Co, as essentially all values were below the limit of quantification of this technique.     

Ultratrace-level radium-226 determination in seawater samples by isotope dilution inductively coupled plasma mass spectrometry

An improved and novel sample preparation method for ²²⁶Ra determination in liquid samples by isotope dilution inductively coupled plasma sector field mass spectrometry using laboratory-prepared ²²⁸Ra tracer has been developed. The procedure involves a selective preconcentration achieved by applying laboratory-prepared MnO₂ resin followed by cation exchange chromatographic separation. In order to completely eliminate possible molecular interferences, medium mass resolution (R = 4,000) combined with chemical separation was found to be a good compromise that enhanced the reliability of the method. The detection limit of 0.084 fg g⁻¹ (3.1 mBq kg⁻¹) achieved is comparable to that of the emanation method or alpha spectrometry and is suitable for low-level environmental measurements. The chemical recovery of the sample preparation method ranged from 72 to 94%. The proposed method enables a rapid, accurate and less labor-intensive approach to routine environmental ²²⁶Ra determination than the radioanalytical techniques conventionally applied.     

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.     

Trace element determination using static high-sensitivity inductively coupled plasma optical emission spectrometry (SHIP-OES)

A low-flow air-cooled inductively coupled plasma (ICP) design for optical emission spectrometry (OES) with axial plasma viewing is described and an evaluation of its analytical capabilities in trace element determinations is presented. Main advantage is a total argon consumption of 0.6 L min⁻¹ in contrast to 15 L min⁻¹ using conventional ICP sources.The torch was evaluated in trace element determinations and studied in direct comparison with a conventional torch under the same conditions with the same OES system, ultrasonic nebulization (USN) and single-element optimization. A variety of parameters (x-y-position of the torch, rf power, external air cooling, gas flow rates and USN operation parameters) was optimized to achieve limits of detection (LOD) which are competitive to those of a conventional plasma source.Ionic to atomic line intensity ratios for magnesium were studied at different radio frequency (rf) power conditions and different sample carrier gas flows to characterize the robustness of the excitation source. A linear dynamic range of three to five orders of magnitude was determined under compromise conditions in multi-element mode. The accuracy of the system was investigated by the determination of Co, Cr, Mn, Zn in two certified reference materials (CRM): CRM 075c (Copper with added impurities), and CRM 281 (Trace elements in rye grass). With standard addition values of 2.44 ± 0.04 and 3.19 ± 0.21 μg g⁻¹ for Co and Mn in the CRM 075c and 2.32 ± 0.09, 81.8 ± 0.4, 32.2 ± 3.9 for Cr, Mn and Zn, respectively, were determined in the samples and found to be in good agreement with the reported values; recovery rates in the 98-108% range were obtained. No influence on the analysis by the matrix load in the sample was observed.     

Optimization of the operating conditions using factorial designs for determination of uranium by inductively coupled plasma optical emission spectrometry

A critical evaluation of the determination of uranium by inductively coupled plasma optical emission spectrometry was performed using factorial designs (2³) involving the factors: acid concentration, radio frequency power and nebulizer gas flow rate. All of the experiments in this study were made for five emission lines, in the presence of nitric and hydrochloric acid. The results demonstrated that, between nitric and hydrochloric acid, the determinations in the presence of nitric acid were most sensitive. The factorial design showed that the nebulizer gas flow rate was the most significant among the factors studied for the five emission lines. Calcium in concentrations of 10 mg L⁻¹ was observed to cause suppression of the emission intensity for some lines. Iron (at least up to 10 mg L⁻¹) did not interfere in the emission intensity of uranium across the five lines studied. Another experiment evaluated simultaneously the effect of 13 other elements, and the results demonstrated that these elements did not affect the emission intensity of uranium for the lines chosen. The optimized method, using the line at 385.957 nm, allows the determination of uranium with limit of quantification of 31 μg L⁻¹ and precision expressed as RSD lower than 2.2% for uranium concentrations of either 500 or 1000 μg L⁻¹. The accuracy was confirmed by analysis of two laboratory reference materials. The developed method was applied to the determination of uranium in an industrial effluent collected from uranium-producing mine in Caetite City, Brazil. The sample was analyzed by inductively coupled plasma mass spectrometry ICP-MS, and the observed recovery was satisfactory.     

Direct multielement trace analyses of silicon carbide powders by spark ablation simultaneous inductively coupled plasma optical emission spectrometry

A procedure for the direct analysis of silicon carbide powders (SiC) by simultaneous detection inductively coupled plasma optical emission spectrometry using a Spectro-CIROS™ spectrometer (CCD-ICP-OES) and a novel spark ablation system Spectro-SASSy (SA) as sample introduction technique is described. The sample preparation procedure for SA of non-conducting material is based on mixing the sample powders with a conducting matrix, in this case copper and briquetting pellets. Pressing time, pressure and mixing ratio are shown to be important parameters of the pelleting technique with respect to their mechanical stability for the reliability of the analysis results. A mixing ratio of 0.2 g +0.6 g for SiC and Cu, a pressure of 10 t cm^− 2 and a pressing time of 8 min have been found optimum. It has also been shown that the spark parameters selected are crucial for uniform volatilization. Electron probe micrographs of the burning spots and the analytical signal magnitude showed that a rather hard spark at 100 Hz was optimum. The determination of trace elements in silicon carbide powders is demonstrated using a calibration based on the addition of standard solutions. For Al, Ti, V, Mn and Fe detection limits in the lower µg g^− 1 range can be achieved. Internal standardization with Y in combination with the addition of standard solutions allows relative standard deviations in the range of 4 to 24% for concentration levels of the order of 3 to 350 µg g^− 1.     

电感耦合等离子体原子发射光谱(ICP-AES)法测定真空精炼镁合金物料中铁、铜、镍

真空精炼是目前镁金属提纯的重要工艺,工艺原料及真空精炼提纯镁金属过程残留物中Fe、Cu、Ni含量的准确测定对工艺参数的优化及调整具有重要的指导作用。传统测定方法中以邻二氮杂菲分光光度法、新亚铜灵分光光度法、丁二酮肟分光光度法测定三种元素含量,结果准确,但操作繁琐,周期较长,难以满足工业生产中高效、快速测定的需要,且方法中所需的有机萃取剂对环境污染较大。本研究选择电感耦合等离子体发射光谱法(ICP-AES)测定真空蒸馏精炼镁合金物料中Fe、Cu、Ni,系统探究了溶解酸、溶解温度、溶解时间对物料溶解和测定的影响,选择了(1+1)盐酸和过氧化氢溶解体系,200℃加热条件下反应20min为最佳消解镁合金原料条件;选择了王水溶解体系,200℃加热条件下反应25min为真空精炼残留物最佳溶解条件。并探讨了ICP-AES测定过程中各元素的检出限和测定下限以及共存元素的干扰情况,建立了ICP-AES测定真空精炼提纯镁合金物料的方法。方法测定结果的相对标准偏差(RSD,n=11)为Fe 5.89%～11.49%、Cu 2.58%～11.78%、Ni 3.36%～11.47%;各元素加标回收率为;Fe 96.35%～102%、Cu 101.3%～108%、Ni 103%～104.7%;按照实验方法测定镁合金原料、真空精炼残留物中的铁、铜、镍,并与国标方法测定结果进行对比,结果相一致。本研究实现了ICP-AES法快速、准确测定真空蒸馏精炼镁合金物料中铁、铜、镍含量,对及时、高效、准确评估真空精炼提纯镁工艺及产品具有重要意义。     

Application of Doehlert designs for optimisation of an on-line preconcentration system for copper determination by flame atomic absorption spectrometry

In the present paper, a system for on-line preconcentration and determination of copper by flame atomic absorption spectrometry (FAAS) was developed. It was based on solid phase extraction of copper(II) ions on a minicolumn of Amberlite XAD-2 loaded with 2-(2-thiazolylazo)-5-dimethylaminophenol (TAM). The optimisation process was carried out using Doehlert designs. Four variables (sampling flow rate, SR; elution flow rate, buffer concentration, BC; and pH) were regarded as factors in the optimisation. The parameter “sensitivity efficiency (SE)” proposed in this paper, and defined as the analytical signal obtained for an on-line enrichment system for a preconcentration time of 1 min was used as analytical response in the optimisation process. Using the established experimental conditions, the proposed on-line system allowed determination of copper with detection limit (3σ/S) of 0.23 μg l⁻¹, and a precision (repeatability), calculated as relative standard deviation (R.S.D.) of 3.9 and 3.7% for copper concentration of 5.00 and 20.00 μg l⁻¹, respectively. The preconcentration factor obtained is 62. The recovery achieved for copper determination in presence of several cations demonstrated that this has enough selectivity for analysis of food samples. The robustness of the proposed system was also evaluated. The accuracy was confirmed by analysis of the following certified reference materials (CRMs): Rice flour NIES 10a, Spinach leaves NIST 1570a, Apples leaves NIST 1515 and Orchard leaves NBS 1571. This procedure was applied for copper determination in natural food samples.     

Oxygen bomb combustion of biological samples for inductively coupled plasma optical emission spectrometry

A rapid sample preparation method is proposed for decomposition of milk powder, corn bran, bovine and fish tissues, containing certified contents of the analytes. The procedure involves sample combustion in a commercial stainless steel oxygen bomb operating at 25 bar. Most of the samples were decomposed within 5 min. Diluted nitric acid or water-soluble tertiary amines 10% v/v were used as absorption solutions. Calcium, Cu, K, Mg, Na, P, S and Zn were recovered with the bomb washings and determined by inductively coupled plasma optical emission spectrometry (ICP-OES). Ethanol mixed with paraffin was used as a combustion aid to allow complete combustion. A cooling step prior releasing of the bomb valve was employed to increase the efficiency of sample combustion. Iodine was also determined in milk samples spiked with potassium iodide to evaluate the volatilization and collection of iodine in amine CFA-C medium and the feasibility of its determination by ICP-OES with axial view configuration. Most of the element recoveries in the samples were between 91 and 105% and the certified and found contents exhibited a fair agreement at a 95% confidence level.     

Silicon determination by inductively coupled plasma atomic emission spectrometry after generation of volatile silicon tetrafluoride

A method for the determination of silicon by inductively coupled plasma atomic emission spectrometry (ICP-AES) is described. The procedure is based on a discontinuous generation of volatile silicon tetrafluoride in concentrated sulphuric acid medium after injecting 125 μl of 0.1%, w/v sodium fluoride solution into 100 μl of the sample. The gaseous silicon tetrafluoride is fed directly into the ICP torch by a flow of 250 ml min⁻¹ Ar carrier gas. The calibration curve was linear up to at least 100 μg ml⁻¹ of Si(IV) and the absolute detection limit was 9.8 ng working with a solution volume of 100 μl. The relative standard deviation for six measurements of 10 μg ml⁻¹ of Si(IV) was 2.32%. The method was applied to the determination of silicon in water and iron ores.     

On-line preconcentration with a novel alkyl phosphinic acid extraction resin coupled with inductively coupled plasma mass spectrometry for determination of trace rare earth elements in seawater

A newly synthesized alkyl phosphinic acid resin (APAR) was used for on-line preconcentration of trace rare earth elements (REES, lanthanides including yttrium) and then determined by inductively coupled plasma mass spectrometry. REEs in seawater could be on-line concentrated on the APAR packed column (4.6 mm i.d. × 50 mm in length), and eluted from the column with 0.5 mL 0.1 mol L⁻¹ nitric acid within 30 s. An enrichment factor of nearly 400 was achieved for all REEs when the seawater sample volume was 200 mL, while the matrix and coexisting spectrally interfering ions such as barium, tin and antimony could be simultaneously separated. The detection limits of this proposed method for REEs were in the range from 1.43 pg L⁻¹ of holmium to 12.7 pg L⁻¹ of lanthanum. The recoveries of REEs were higher than 97.9%, and the precision of the relative standard deviation (R.S.D., n = 6) was less than 5%. The method has been applied to the determination of soluble REEs in seawater.     

Application of wavelet transform to background correction in inductively coupled plasma atomic emission spectrometry

A background correction method based on wavelet transform was devised and applied to inductively coupled plasma atomic emission spectrometry (ICP-AES). The proposed approach separated background from analyte signal according to their different frequencies. Compared with the analyte signal, the background has a low frequency. By removal of the components attributed to the signal, the background over the spectral window of the analyte line can be fitted through wavelet reconstruction. The results showed that the wavelet transform technique could handle all kinds of background and low signal-to-background ratio spectra, and required no prior knowledge about the sample composition, no selection of suitable background correction points, and no mathematical assumption of the background distribution. This technique performed as well as the conventional three-point background correction method for linear backgrounds, and provided better results than the latter for curved backgrounds. The proposed procedure was illustrated, by processing real spectra, to be an effective and practical tool for background correction in ICP-AES.     

Field-flow fractionation: An efficient approach for matrix removal of soil extract for inductively coupled plasma optical emission spectrometry

An on-line coupling between a continuous-flow sequential extraction (CFSE) unit and flow field-flow fractionation with cross flow matrix removal (FlFFF/CFM) with ICP-OES detection was developed for determination of metal leachability from soil. The use of high concentration of Mg(NO₃)₂ in exchangeable phase can cause undesirable matrix effects by shifting ionization equilibrium in the plasma, etc., resulting in a clear need for matrix removal. Therefore, the capability of FlFFF/CFM to remove Mg matrix ion from soil extract was evaluated. Poly(ethylene imine) (PEI) having molecular weight of 25,000 Da was added to form complexes with analyte elements (Cu, Mn, Pb, and Zn) but not the matrix element (Mg). The free Mg matrix ions were then removed by filtering off through the ultrafiltration membrane, having a 1000-Da molecular weight cut-off, inside the FlFFF channel. With the use of FlFFF/CFM, matrix removal efficiency was approximately 83.5%, which was equivalent to approximately 6-fold dilution of the matrix ion. The proposed hyphenated system of CFSE and FlFFF/CFM with ICP-OES detection was examined for its reliability by checking with SRM 2710 (a highly contaminated soil from Montana). The metal contents determined by the proposed method were not significantly different (at 95% confidence) from the certified values.