Hollow-fiber liquid-phase microextraction prior to low-temperature electrothermal vaporization ICP-MS for trace element analysis in environmental and biological samples

A new method of hollow-fiber liquid-phase microextraction (HF-LPME) prior to electrothermal vaporization (ETV) inductively coupled plasma mass spectrometry (ICP-MS) determination of trace Cu, Zn, Pd, Cd, Hg, Pb and Bi, based on gaseous compounds introduction into the plasma as their diethyldithiocarbmate (DDTC) chelates, was developed. The use of the reagent DDTC as chemical modifier could not only enhance the analytical signals, but also decrease the vaporization temperature. At a temperature of 1300 degrees C, trace Cu, Zn, Pd, Cd, Hg, Pb and Bi can be vaporized completely into the ICP. The factors affecting the formation of the chelates and their vaporization behaviors were investigated in detail, and the microextraction conditions were optimized. Under the optimized conditions, the detection limits of the proposed method were 12.4, 28.7, 7.9, 4.5, 3.3, 4.8 and 1.6 pg ml(-1) for Cu, Zn, Pd, Cd, Hg, Pb and Bi, respectively. Enrichment factors of 305, 284, 24, 29, 20, 73 and 43 could be achieved within 15 min of extraction time, and the relative standard deviations (RSDs) for the seven determinations of 0.5 ng ml(-1) of target analytes were 8.8, 6.9, 7.1, 9.4, 10.2, 6.1 and 10.8%, respectively. The newly developed method has been applied to the determination of trace Cu, Zn, Pd, Cd, Hg, Pb and Bi in environmental water and human serum samples, and the recoveries for the spiked samples were in the range of 88-116%. In order to validate this method, two certified reference materials, GBW08501 peach leaves and GBW(E)080040 seawater, were analyzed, and the determined values were in good agreement with the certified values.     

Solvent bar microextraction combined with electrothermal vaporization inductively coupled plasma mass spectrometry for the speciation of inorganic arsenic in water samples

A new method of solvent bar microextraction (SBME) combined with electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) for the speciation of As(III) and As(V) in water samples was developed. The method is based on the chelation of As(III) and ammonium pyrrolidine dithiocarbamate (APDC) under the selected conditions, and the As(III)-PDC complex could be extracted into the organic phase, while As(V) remained in aqueous solution. The post-extraction organic phase was directly injected into ETV-ICP-MS for determination of As(III) with the use of iridium as permanent chemical modifier. As(V) was reduced to As(III) by L-cysteine and was then subjected to SBME prior to total As determination. The assay of As(V) was based on subtracting As(III) from total As. The factors affecting on the SBME, such as organic solvent, sample pH, chelating reagent concentration, stirring rate and extraction time, and chemical modification of iridium in ETV-ICP-MS have been studied. Under the optimized conditions, the enrichment factor of 220-fold could be achieved in 15 min extraction, the limit of detection (LOD) for As(III) was 0.32 pg mL^− 1, and the relative standard deviation (RSD) was 8.8% (0.1 ng mL^− 1, n = 9). Compared with hollow fiber liquid phase microextraction (HF-LPME), SBME has a higher enrichment factor and faster extraction kinetics. In order to validate the accuracy of the method, a Certified Reference Material of GSBZ50004-88 (No. 200420) water sample was analyzed and the results obtained were in good agreement with the certified values. The developed method was also applied to the speciation of inorganic As in environmental waters with satisfactory results.     

Optimization of a single-drop microextraction method for multielemental determination by electrothermal vaporization inductively coupled plasma mass spectrometry following in situ vapor generation

A headspace single-drop microextraction (HS-SDME) method has been developed in combination with electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) for the simultaneous determination of As, Sb, Bi, Pb, Sn and Hg in aqueous solutions. Vapor generation is carried out in a 40 mL volume closed-vial containing a solution with the target analytes in hydrochloric acid and potassium ferricyanide medium. Hydrides (As, Sb, Bi, Pb, Sn) and Hg vapor are trapped onto an aqueous single drop (3 µL volume) containing Pd(II), followed by the subsequent injection in the ETV. Experimental variables such as medium composition, sodium tetrahydroborate (III) volume and concentration, stirring rate, extraction time, sample volume, ascorbic acid concentration and palladium amount in the drop were fully optimized. The limits of detection (LOD) (3σ criterion) of the proposed method for As, Sb, Bi, Pb, Sn and Hg were 0.2, 0.04, 0.01, 0.07, 0.09 and 0.8 µg/L, respectively. Enrichment factors of 9, 85, 138, 130, 37 and 72 for As, Sb, Bi, Pb, Sn and Hg, respectively, were achieved in 210 s. The relative standard deviations (N = 5) ranged from 4 to 8%. The proposed HS-SDME-ETV-ICP-MS method has been applied for the determination of As, Sb, Bi, Pb, Sn and Hg in NWRI TM-28.3 certified reference material.     

Determination of the rare earth elements La, Eu, and Yb using solidified floating organic drop microextraction and electrothermal vaporization ICP-MS

We have developed a method for the determination of trace levels of the rare earth elements La, Eu, and Yb in biological and environmental samples. It is based on solidified floating organic drop microextraction using 1-(2-pyridylazo)-2-naphthol (PAN) as a chelator, followed by electrothermal vaporization (ETV) and quantification by inductively coupled plasma mass spectrometry. PAN also acts as a modifier in ETV. The effects of pH, amount of PAN, extraction time, stirring rate, volume of sample solution, and temperature program were examined. Under optimized conditions, the detection limits are 2.1, 0.65 and 0.91 pg mL^?1 for the elements La, Eu and Yb, respectively. The relative standard deviations are <6.0 % (c?=?0.1 ng mL^?1, n?=?9). When applied to the analysis of (spiked) natural water samples, the recoveries range from 92 to 105 %. The accuracy was validated with certified reference materials (combined sample of branch and leaf of shrub: GBW 07603 and human hair: GBW 07601), and the results were in good agreement with the certified values.

Evaluation of pyrolysis curves for volatile elements in aqueous standards and carbon-containing matrices in electrothermal vaporization inductively coupled plasma mass spectrometry

Pyrolysis curves in electrothermal atomic absorption spectrometry (ET AAS) and electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) have been compared for As, Se and Pb in lobster hepatopancreas certified reference material using Pd/Mg as the modifier. The ET AAS pyrolysis curves confirm that the analytes are not lost from the graphite furnace up to a pyrolysis temperature of 800 °C. Nevertheless, a downward slope of the pyrolysis curve was observed for these elements in the biological material using ETV-ICP-MS. This could be related to a gain of sensitivity at low pyrolysis temperatures due to the matrix, which can act as carrier and/or promote changes in the plasma ionization equilibrium. Experiments with the addition of ascorbic acid to the aqueous standards confirmed that the higher intensities obtained in ETV-ICP-MS are related to the presence of organic compounds in the slurry. Pyrolysis curves for As, Se and Pb in coal and coal fly ash were also investigated using the same Pd/Mg modifier. Carbon intensities were measured in all samples using different pyrolysis temperatures. It was observed that pyrolysis curves for the three analytes in all slurry samples were similar to the corresponding graphs that show the carbon intensity for the same slurries for pyrolysis temperatures from 200 °C up to 1000 °C.     

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 2.9 pg mL⁻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.     

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.     

Electrothermal vaporization inductively coupled plasma mass spectrometry for the determination of trace amount of lanthanides and yttrium in soil with polytetrafluroethylene emulsion as a chemical modifier

A method of electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) for the determination of trace lanthanides and yttrium in soil samples with a polytetrafluorethylene (PTFE) emulsion as chemical modifier to promote the vaporization of the analytes from the graphite furnace was developed in this paper. The analytical characteristics, spectral interference and matrix effect of the analytical method were evaluated and critically compared with those of pneumatic nebulization inductively coupled plasma mass spectrometry (PN-ICP-MS). Under the optimized operation conditions, the relative detection limits of lanthanides (La-Lu) and yttrium for ETV-ICP-MS and PN-ICP-MS were 0.4-20 ng l⁻¹ and 1.0-21 ng l⁻¹, respectively, the absolute detection limits for ETV-ICP-MS were 4-200 fg, which were improved by 1-2 orders of magnitude compared with PN-ICP-MS. While the analytical precision of ETV-ICP-MS is worse than that of PN-ICP-MS, with the R.S.D.s (%) of 4.1-10% for the former and 2.9-7.8% for the latter. Regarding to the matrix effect, both conventional method and stepwise dilution method were employed to observe the effect of matrix and the very similar results were obtained. It was found that the highest tolerance concentration of the matrix is 1000 mg l⁻¹ and 800 mg l⁻¹ for ETV-ICP-MS and PN-ICP-MS, respectively. To assess the accuracy, the proposed method was applied to the determination of trace lanthanides and yttrium in three different soil standard reference materials and one soil sample, and the determined values are in good agreement with the certified values or reference values.     

Determination of As, Ge, Hg, Pb, Sb, Se and Sn in coal slurries by CVG-ETV-ICP-MS using external or isotopic dilution calibration

A method for the multi-elemental determination of As, Ge, Hg, Pb, Sb, Se and Sn in coal reference materials by slurry sampling chemical vapor generation (CVG) using external calibration and isotopic dilution (ID) calibration and detection by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) is proposed. As, Ge, Sb, Se and Sn were determined using the external calibration, while, Hg, Pb, Se and Sn were determined by isotopic dilution. About 50–250 mg of sample was mixed with an acid solution, containing aqua regia and HCl, in an ultrasonic bath. For the isotopic dilution calibration, the enriched isotopes ²⁰¹Hg, ²⁰⁶Pb, ⁷⁷Se and ¹¹⁹Sn were added to the slurry in an adequate amount in order to produce an altered isotopic ratio close to 1. The vapor produced by the reaction of the sample slurry with the reducing agent was transported to the vaporizer and trapped in a Ir-treated graphite tube at 200 °C, before vaporization at 2100 °C and transportation of the vapor to the plasma. The accuracy of the method was assured by the analysis of four certified reference coal samples, using external calibration with aqueous solutions, prepared in the same medium and subjected to the same CVG and trapping procedure as the slurries and also by isotopic dilution calibration. The obtained concentrations were in agreement with the certified values, using the t-Student test for a confidence level of 95%. The detection limits (3 s; n = 5) of isotopic dilution, in ng g^− 1, were: 0.4 for Hg, 900 for Pb, 0.3 for Se and 0.2 for Sn. For external calibration, the detection limits, in ng g^− 1, were: 1.6 for As, 0.1 for Ge, 0.3 for Sb, 0.9 for Se and 7.5 for Sn. The relative standard deviations generally were lower than 14%, adequate for slurry analysis.     

Determination of the rare earth elements La,Eu, and Yb using solidified floating organic drop microextraction and electrothermal vaporization ICP-MS

We have developed a method for the determination of trace levels of the rare earth elements La, Eu, and Yb in biological and environmental samples. It is based on solidified floating organic drop microextraction using 1-(2-pyridylazo)-2-naphthol (PAN) as a chelator, followed by electrothermal vaporization (ETV) and quantification by inductively coupled plasma mass spectrometry. PAN also acts as a modifier in ETV. The effects of pH, amount of PAN, extraction time, stirring rate, volume of sample solution, and temperature program were examined. Under optimized conditions, the detection limits are 2.1, 0.65 and 0.91 pg mL⁻¹ for the elements La, Eu and Yb, respectively. The relative standard deviations are <6.0 % (c = 0.1 ng mL⁻¹, n = 9). When applied to the analysis of (spiked) natural water samples, the recoveries range from 92 to 105 %. The accuracy was validated with certified reference materials (combined sample of branch and leaf of shrub: GBW 07603 and human hair: GBW 07601), and the results were in good agreement with the certified values.

►Solidified floating organic drop microextraction was combined with ETV for ICP-MS. ►PAN acted as both a chelating agent and a chemical modifier. ►The method was used for analysis of rare earth elements in real samples. ►The method has the merits of low detection limit, good precision and accuracy.

     

Dispersive liquid phase microextraction (DLPME) combined with graphite furnace atomic absorption spectrometry (GFAAS) for determination of trace Co and Ni in environmental water and rice samples

A new method of dispersive liquid phase microextraction (DLPME) combined with graphite furnace atomic absorption spectrometry (GFAAS) was proposed for the determination of trace Co and Ni using 1-(2-pyridylazo) 2-naphthol (PAN) as chelating reagent. Several factors influencing the microextraction efficiency of Co and Ni and their subsequent determinations, such as pH, extraction and disperser solvent type and their volume, concentration of the chelating agent, extraction time and ashing temperature and atomization temperature were studied, and the optimized experimental conditions were established. After extraction, the enrichment factors were 101 and 200 for Co and Ni, respectively. The detection limits of the method were 21 and 33 pg/mL for Co and Ni, and the relative standard deviations (R.S.Ds.) for five determinations of 0.5 ng/mL Co and Ni were 7.5% and 8.2%, respectively. The results for the determination of Co and Ni in East Lake water, Yangtse River water, Dongbei rice and spiked samples have demonstrated the accuracy, recovery and applicability of the proposed method. To validate the proposed method, two certified reference materials of Environment Water (GSBZ50009-88) and NIES No.10-b rice flour were analyzed, and the determined values were in good agreement with the certified values.     

Determination of some refractory elements and Pb by fluorination assisted electrothermal vaporization inductively coupled plasma mass spectrometry with platform and wall vaporization

Platform and wall vaporization for electrothermal vaporization (ETV)-inductively coupled plasma mass spectrometry (ICP-MS) determination of some refractory elements (Ti, V, Cr, Mo, La and Zr) and Pb were comparatively studied with the use of poly (tetrafluoroethylene) (PTFE) as fluorinating reagent. The factors affecting the vaporization behaviors of the target analytes in the platform and tube wall vaporization including vaporization temperature and time, pyrolytic temperature and time were studied in detail, and the flow rates of carrier gas/auxiliary carrier gas, were carefully optimized. Under the optimal conditions, the signal profiles, signal intensity, interferences of coexisting ions and analytical reproducibility for wall and platform vaporization ETV-ICP-MS were compared. It was found that both wall and platform vaporization could give very similar detection limits, but the platform vaporization provided higher signal intensity and better precision for some refractory elements and Pb than the wall vaporization. Especially for La, the signal intensity obtained by platform vaporization was 3 times higher than that obtained by wall vaporization. For platform vaporization ETV-ICP-MS, the limits of detection (LODs) of 0.001 μg L⁻¹ (La) ~ 0.09 μg L^− 1 (Ti) with the relative standard deviations (RSDs) of 1.5% (Pb) ~ 15.5% (Zr) were obtained. While for wall vaporization ETV-ICP-MS, LODs of 0.005 μg L^− 1 (La) ~ 0.4 μg L^− 1 (Pb) with RSDs of 3.2% (Mo) ~ 12.8% (Zr) were obtained. Both platform and tube wall vaporization techniques have been used for slurry sampling fluorination assisted ETV-ICP-MS direct determination of Ti, V, Cr, Mo, La, Zr and Pb in certified reference materials of NIES No. 8 vehicle exhaust particulates and GBW07401 soil, and the analytical results obtained are in good agreement with the certified values.     

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.     

Determination of volatile elements in biological materials by isotopic dilution ETV-ICP-MS after dissolution with tetramethylammonium hydroxide or acid digestion

Isotopic dilution for the determination of Ag, Cd, Hg, Pb and Tl in biological materials by ETV-ICP-MS is proposed. The sample was simply dissolved with tetramethylammonium hydroxide (TMAH) or acid digested in a microwave furnace, with an on line matrix separation. When the dissolution was employed, Ir was used as a chemical modifier for Hg and Pb and Pd was used for Cd and Tl. No modifier was used for Ag. The pyrolysis temperatures were taken from pyrolysis temperature curves. The on line preconcentration was performed in a flow injection system with solenoid valves and was based on the analyte complexation with ammonium diethyldithiophosphate and sorption of the complexes on C(18) bonded to silica gel in a minicolumn. For the digested sample submitted to the analyte preconcentration procedure, a modifier, Ir, was only used for Hg. For the other analytes, since a low pyrolysis temperature, 300 degrees C, was employed, no modifier was added. The isotopic dilution calibration was applied to two certified materials, bovine liver and dog fish muscle, dissolved with TMAH or acid digested, and to another two certified materials, corn bran and rice flour, acid digested and submitted to analyte preconcentration. The obtained concentration values agree with the certified ones, showing that this calibration procedure leads to accurate results in the determination of low concentrations of volatile elements. Due to simplicity, the dissolution with TMAH is very attractive.     

Studies on transport phenomena in electrothermal vaporization sample introduction applied to inductively coupled plasma for optical emission and mass spectrometry

In the present work electrothermal vaporization (ETV) was used in both inductively coupled plasma mass spectrometry (ICP-MS) and optical emission spectrometry (OES) for sample introduction of solution samples. The effect of (Pd + Mg)-nitrate modifier and CaCl₂ matrix/modifier of variable amounts were studied on ETV-ICP-MS signals of Cr, Cu, Fe, Mn and Pb and on ETV-ICP-OES signals of Ag, Cd, Co, Cu, Fe, Ga, Mn and Zn. With the use of matrix-free standard solutions the analytical curves were bent to the signal axes (as expected from earlier studies), which was observed in the 20–800 pg mass range by ICP-MS and in the 1–50 ng mass range by ICP-OES detection. The degree of curvature was, however, different with the use of single element and multi-element standards. When applying the noted chemical modifiers (aerosol carriers) in microgram amounts, linear analytical curves were found in the nearly two orders of magnitude mass ranges. Changes of the CaCl₂ matrix concentration (loaded amount of 2–10 μg Ca) resulted in less than 5% changes in MS signals of 5 elements (each below 1 ng) and OES signals of 22 analytes (each below 15 ng). Exceptions were Pb (ICP-MS) and Cd (ICP-OES), where the sensitivity increase by Pd + Mg modifier was much larger compared to other elements studied. The general conclusions suggest that quantitative analysis with the use of ETV sample introduction requires matrix matching or matrix replacement by appropriate chemical modifier to the specific concentration ranges of analytes. This is a similar requirement to that claimed also by the most commonly used pneumatic nebulization of solutions, if samples with high matrix concentration are concerned.     

Determination of cadmium,mercury and lead in seawater by electrothermal vaporization isotope dilution inductively coupled plasma mass spectrometry

Electrothermal vaporization isotope dilution inductively coupled plasma mass spectrometry (ETV-ID-ICP-MS) has been applied to the determination of Cd, Hg and Pb in seawater samples. The isotope ratios of the elements studied in each analytical run were calculated from the peak areas of each isotope. Various modifiers were tested for the best signal of these elements. After preliminary studies, 0.15% m/v TAC and 4% v/v HCl were added to the sample solution to work as the modifier. The ETV-ID-ICP-MS method has been applied to the determination of Cd, Hg and Pb in NASS-4 and CASS-3 reference seawater samples and seawater samples collected from Kaohsiung area. The results for reference sample NASS-4 and CASS-3 agreed satisfactorily with the reference values. Results for other samples determined by isotope dilution and method of standard additions agreed satisfactorily. Detection limits were approximately 0.002, 0.005 and 0.001 ng ml⁻¹ for Cd, Hg and Pb in seawater, respectively, with the ETV-ICP-MS method. Precision between sample replicates was better than 20% for most of the determinations.     

Vaporization of Pb,As and Ga alone and in the presence of Pd modifier studied by electrothermal vaporization-inductively coupled mass spectrometry

Inductively coupled plasma mass spectrometry (ICP-MS) with electrothermal vaporization (ETV) was used to study the processes taking place in a graphite furnace for atomic spectroscopy. Monitoring of carbon release during the pyrolysis stage provided information on the solid-state reduction processes. Among three carbon species studied (¹²C, ¹³C and ²⁸CO), ¹³C was found to be the most suitable. Gallium and arsenic oxides practically do not reduce during the pyrolysis stage. According to the data on carbon release, two reduction processes of lead species (at about 690–915 and > 1000 °C) were found to take place in the furnace. Two separate peaks of Pb (at the end of the pyrolysis stage and in the vaporization stage) were observed, probably related to vaporization of unreduced lead oxide and elemental Pb, respectively. A pre-reduced palladium modifier suppresses the low-temperature Pb losses so that the high-temperature Pb peak is increased. In the absence of modifier, a gaussian-shaped As signal was formed only if small arsenic masses were introduced into the vaporizer. Increase of the arsenic mass resulted in formation of a pronounced plateau after the peak, in spite of the very high vaporization temperature applied (2500 °C). In the presence of pre-reduced palladium modifier, a gaussian-shaped As signal was formed already at 1700 °C with a 4–15-fold increase in sensitivity depending on the analyte mass. The palladium modifier apparently prevents strong interaction of arsenic with graphite. The obtained data support very high potential of ETV-ICP-MS for detailed investigation of processes occurring in graphite furnaces used in analytical atomic spectroscopy, especially during the pyrolysis stage.     

Selective determination of inorganic cobalt in nutritional supplements by ultrasound-assisted temperature-controlled ionic liquid dispersive liquid phase microextraction and electrothermal atomic absorption spectrometry

In the present work, a simple and rapid analytical method based on application of ionic liquids (ILs) for inorganic Co(II) species (iCo) microextraction in a variety of nutrient supplements was developed. Inorganic Co was initially chelated with 1-nitroso-2-naphtol (1N2N) reagent followed by a modern technique named ultrasound-assisted temperature-controlled ionic liquid dispersive liquid phase microextraction (USA-TILDLME). The extraction was performed with 1-hexyl-3-methylimidazolium hexafluorophosphate [C₆mim][PF₆] with the aid of ultrasound to improve iCo recovery. Finally, the iCo-enriched IL phase was solubilized in methanol and directly injected into an electrothermal atomic absorption spectrometer (ETAAS). Several parameters that could influence iCo microextraction and detection were carefully studied. Since the main difficulty in these samples is caused by high concentrations of potential interfering ions, different approaches were evaluated to eliminate interferences. The limit of detection (LOD) was 5.4 ng L^?1, while the relative standard deviation (RSD) was 4.7% (at 0.5 μg L^?1 Co level and n = 10), calculated from the peak height of absorbance signals. Selective microextraction of iCo species was achieved only by controlling the pH value during the procedure. The method was thus successfully applied for determination of iCo species in nutritional supplements.     

Direct inductively coupled plasma-atomic emission spectrometry analysis of trace elements in muscle tissues of hairtail using electrothermal vaporization with slurry sampling

A procedure for direct determination of trace elements in muscle tissue of hairtail was developed using inductively coupled plasma-atomic emission spectrometry and electrothermal vaporization with slurry sampling. Due to use of polytetrafluoroethylene as the chemical modifier, the vaporization behaviors of analytes from the slurry and the aqueous standard solutions were very similar. In this case, the aqueous standards could be used for the calibration of slurry samples. The main factors influencing this method were studied systematically. The detection limits for Cr, Ni, Zn, Cd, and Pb were 3.1, 10.5, 176, 6.9, and 83 ng/mL, respectively, and the relative standard deviations were less than 10%. The proposed method was applied to the determination of trace Cr, Ni, Zn, Cd, and Pb in hairtail samples with satisfactory accuracy and precision. A certified reference material of mussel (GBW 08571) was analyzed, and good agreement was obtained between the results from the proposed method and certificate values.     

Solid phase extraction for analysis of biogenic carbonates by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS): an investigation of rare earth element signatures in otolith microchemistry

Uptake of trace elements into fish otoliths is governed by several factors such as life histories and environment in addition to stock and species differences. In an attempt to elucidate the elemental signatures of rare earth elements (REEs) in otoliths, a solid phase extraction (SPE) protocol was used in combination with electrothermal vaporization (ETV) as a sample introduction procedure for the determinations by inductively coupled plasma quadrupole mass spectrometry (ICP-MS). Effects of various parameters, such as carrier gas flow rate, atomization temperature and chemical modification, were examined for optimization of the conditions by ETV-ICP-MS. Atomization was achieved at 2800 °C. Lower temperatures (i.e. 2600 °C) resulted in severe memory problems due to incomplete atomization. Palladium was used as a chemical modifier. It was found that an increase in Pd concentration up to 0.5 μg in the injection volume (70 μl) led up to four-fold enhancement in the integrated signals. This phenomenon is attributed to the carrier effect of Pd rather than the stabilization since no significant losses were observed for high temperature drying around 700 °C even in the absence of Pd. Preconcentration was performed on-line at pH 5 by using a mini-column of Toyopearl AF-Chelate 650M chelating resin, which also eliminated the calcium matrix of otolith solutions. After preconcentration of 6.4 ml of solution, the concentrate was collected in 0.65 ml of 0.5% (v/v) HNO₃ in autosampler cups, and then analyzed by ETV-ICP-MS. The method was validated with the analysis of a fish otolith certified reference material (CRM) of emperor snapper, and then applied to samples. Results obtained from otoliths of fish captured in the same habitat indicated that otolith rare earth element concentrations are more dependent on environmental conditions of the habitat than on species differences.