A pilot study on the feasibility of the preparation of a new certified reference material based on the Antarctic Scallop Adamussium Colbecki

As foreseen by the Italian National Programme of Research in Antarctica, a preliminary investigation was performed to ascertain the feasibility of the production of a new Certified Reference Material for trace elements based on the bivalve Adamussium colbecki. The scallops sampled in Antarctica during the 1999–2000 Italian scientific expedition were analyzed by inductively coupled plasma atomic emission spectrometry and high-resolution inductively coupled plasma mass spectrometry for their content in selected trace elements (As, Cd, Cr, Cu, Fe, Hg, Mn, Mo, Ni, V and Zn). The certification campaign will be undertaken on the basis of the findings of this feasibility study in close cooperation with the Institute for Reference Materials and Measurements, Joint Research Centre of the European Commission.     

Application of isotope-dilution laser ablation ICP–MS for direct determination of Pu concentrations in soils at pg g<Superscript>−1</Superscript> levels

The methods available for determination of environmental contamination by plutonium at ultra-trace levels require labor-consuming sample preparation including matrix removal and plutonium extraction in both nuclear spectroscopy and mass spectrometry. In this work, laser-ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) was applied for direct analysis of Pu in soil and sediment samples. Application of a LINA-Spark-Atomizer system (a modified laser ablation system providing high ablation rates) coupled with a sector-field ICP–MS resulted in detection limits as low as 3×10^–13 g g^–1 for Pu isotopes in soil samples containing uranium at a concentration of a few g g^–1. The isotope dilution (ID) technique was used for quantification, which compensated for matrix effects in LA–ICP–MS. Interferences by UH⁺ and PbO₂⁺ ions and by the peak tail of ²³⁸U⁺ ions were reduced or separated by use of dry plasma conditions and a mass resolution of 4000, respectively. No other effects affecting measurement accuracy, except sample inhomogeneity, were revealed. Comparison of results obtained for three contaminated soil samples by use of -spectrometry, ICP–MS with sample decomposition, and LA–ICP–IDMS showed, in general, satisfactory agreement of the different methods. The specific activity of ^239+240Pu (9.8±3.0 mBq g^–1) calculated from LA–ICP–IDMS analysis of SRM NIST 4357 coincided well with the certified value of 10.4±0.2 mBq g^–1. However, the precision of LA–ICP–MS for determination of plutonium in inhomogeneous samples, i.e. if "hot" particles are present, is limited. As far as we are aware this paper reports the lowest detection limits and element concentrations yet measured in direct LA–ICP–MS analysis of environmental samples.Sergei F. Boulyga is on leave from The Radiation Physics and Chemistry Problems Institute, 220109 Sosny, Minsk, Belarus.     

Application of routine estimation of Pb isotopic ratios by inductively coupled plasma mass spectrometry for studying the Pb origin in hair of children living in polluted areas. A pilot study

The analysis of ²⁰⁴Pb, ²⁰⁶Pb, ²⁰⁷Pb and ²⁰⁸Pb isotope ratios for environmental Pb markers (leaded gasoline, air-borne particulate matter, house window dust) and hair of children was undertaken by the routine quadrupole inductively coupled argon plasma mass spectrometry (Q-ICP-MS). Hair samples collected from 10-year-old children living in Krakow in 1995 and 35 randomly selected children, aged 11, both sexes were included in the current study. Air-borne particles were collected by PM-2.5 (an aerodynamic diameter dac <2.5 μm) and PM-10 (fraction with an dac <10 μm) samplers in the proximity of steel factories situated near Krakow. Imprecision of routine estimations was approximately 0.6–0.7% or less, and was the lowest for the ²⁰⁷Pb/²⁰⁸Pb ratio (approx. 0.2%). These conditions were sufficient to distinguish Pb from air-borne dust from that in gasoline or window dust. No differences were found between Pb in PM-2.5 and PM-10 particles. The associations of the Pb in the these environmental sources and that in hair of children were discussed. The relationships of the Pb isotope ratios and other parameters related to environmental pollution were also analyzed. The analysis of distribution of the ²⁰⁷Pb/²⁰⁸Pb ratio in the hair of children, provided some evidence of the fact that hair lead of approximately 20% of the investigated population could arise from gasoline, while the Pb from air-borne dust and remaining sources can be attributed to approximately 80% of the population.     

Determination of the absolute configuration of selenomethionine from antarctic krill by RP-HPLC/ICP-MS using chiral derivatization agents

A fast and sensitive method was developed for the determination of the absolute configuration of selenomethionine. The enantiomers of selenomethionine were converted into diastereomeric isoindole derivatives by reaction with o-phthaldialdehyde and N-isobutyryl-l-cysteine. This easy-to-handle reaction proceeds quantitatively in a few minutes at room temperature. Separation and detection of the diastereomers was achieved by reversed-phase high-performance liquid chromatography–inductively coupled plasma-mass spectrometry (RP-HPLC/ICP-MS) using a conventional C18 reversed-phase column. Detection limits of about 4 µg L^–1 were obtained. The method was applied to the determination of the configuration of selenomethionine extracted from antarctic krill, which turned out to possess the l-configuration.     

Direct analysis of fly ash materials by inductively coupled plasma atomic emission spectrometry using slurry nebulization

Fly ash samples of cement works were analysed using slurry nebulization inductively coupled plasma atomic emission spectrometric (ICP-AES). Because of the influence of the experimental factors on the signal intensity, the optimal conditions of the analysis circumstances were determined. Control analyses (wet digestion followed by ICP-AES, and XRF of dry powders (pressed pellets)) were also carried out to compare the results. Based on the result, it was concluded that the slurry nebulization method using slurry standard of same type reference material for calibration can be applied for rapid but less precise (RSD 5–10%) determination of the elements in fly ash.     

Determination of trace element in Italian virgin olive oils and their characterization according to geographical origin by statistical analysis

Multi-element analysis of organic virgin olive oils from different Italian regions was carried out by inductively coupled plasma mass spectrometry (ICP-MS) aiming at developing a reliable method in the traceability of the origin of oils. The data were processed by means of the chemiometric approach of linear discriminant analysis (LDA) that allows classifying unknown samples after checking possible differentiation of samples of known origin.An external calibration curve was build for the quantitative analysis. The calibration curves for each element were linear in the range between 0.01 and 100 ng mL⁻¹ and 0.2 to 2000 ng mL⁻¹, the correlation coefficients were ranging between 0.996 and 0.999. Results from spike and recovery experiments at levels of 30 and 65 ng mL⁻¹ were in the range of 91-119%, whereas the quantitation limits, based on 10 times standard deviation of the blank, were also in the range of 0.009-10.2 ng g⁻¹, for almost all the elements.     

Capillary electrophoresis inductively coupled plasma mass spectrometry

Chemical speciation (extraction of elemental information and identification of molecular environment for an analyte in a complex sample) has been a long sought after goal for analytical chemists. Recently, because of successful developments in more sensitive element-specific detectors and gentle separation schemes, which preserve the true chemical information in a real sample, routine speciation experiments are becoming a common occurrence in the scientific literature. For many reasons, the combination of capillary electrophoresis (for separation of different chemical species) with inductively coupled plasma mass spectrometry (for element and isotope specific detection) has emerged as the method of choice for these analyses. In this article the basic principles of capillary electrophoresis inductively coupled plasma mass spectrometry are discussed. Design consideration for instrument interface, anticipated difficulties with speciation experiments and applications for specific matrices and analytes are also presented in this article.     

Determination of cadmium in polyethylene by analytical atomic spectrometry with gas-phase sample introduction technique

Cadmium in polyethylene was determined by both inductively coupled plasma atomic emission spectrometry (ICP-AES) and atomic absorption spectrometry (AAS) with continuous-flow gas-phase sample introduction in a reaction medium of ascorbic acid. In the presence of mixture of cobalt and thiourea in the ascorbic acid solution, the sensitivities by both ICP-AES and AAS for cadmium were greatly enhanced. The gaseous cadmium species was phase-separated in a gas–liquid separator and directed via a stream of argon carrier gas to an inductively coupled plasma and an electrically heated quartz tube atomizer (QTA) for atomic spectrometry. Under the optimized experimental conditions, the best attainable detection limits at Cd I 228.802 nm line were 1.3 and 0.017 ng/ml with linear dynamic ranges of 10–500 ng/ml and 0.1–1 ng/ml in concentrations by ICP-AES and QTA-AAS, respectively. The instrumental precisions expressed as the relative standard deviation (R.S.D.) from ten replicate measurements of 50 and 1 ng/ml cadmium by ICP-AES and QTA-AAS were 5.6% and 3.2%, respectively. With the use of ICP-AES and QTA-AAS with gas-phase sample introduction method, six- and 200-fold improvements in detection limits for cadmium were obtained in comparison with their conventional solution nebulization methods, respectively. After the effects of several diverse elements on the determination of cadmium by ICP-AES and QTA-AAS with the present gas-phase sample introduction systems were examined, these methods were applied to the determination of low concentrations of cadmium in polyethylene. The results obtained by the present method were in good agreement with the certified values.     

Determination of cadmium, lead, iron, nickel and chromium in selected food matrices by plasma spectrometric techniques

In the frame of a study aimed at investigating the transfer of metal contaminants through the food chain and the effects of food processing, five elements, namely Cd, Pb, Fe, Ni and Cr, were accurately determined in (i) durum wheat grain and derived products, (ii) wheat-based reference materials, (iii) drinking water, used both as an ingredient and for technological purposes in the investigated industrial process. Microwave closed vessel digestion was selected as the dissolution technique for solid samples, whereas water samples were acidified with ultrapure nitric acid and analysed directly. As several analytes had to be quantified at trace or ultratrace levels, inductively coupled plasma mass spectrometry (ICP-MS) was resorted to for analytical determinations. Overall, this straightforward analytical approach enabled to detect the often small changes in element concentration associated with the different technological steps of processing. Nevertheless, detection of heavily interfered elements, especially Cr, as well as analyte quantification at ultratrace-level level in water, posed analytical challenges that required suited analytical solutions.Changes in the sample introduction system and complementary use of inductively coupled plasma atomic emission spectrometry (ICP-AES) straightforwardly overcame the difficulties in determining the analytes in the selected food matrixes. The benefits of ultrasonic nebulization in reducing the effects of problematic spectral interferences were demonstrated. Overall, a robust and high-throughput analytical method was outlined.     

Analytical evaluation of electrothermal vaporization/low-pressure inductively coupled plasma atomic emission spectrometry for trace elemental analysis in microliter samples

A novel method for the determination of trace elements in microliter samples using the tantalum filament electrothermal vaporization/low-pressure inductively coupled plasma (ETV/LP-ICP) atomic emission spectrometry has been developed. An improved tantalum filament ETV was directly coupled with LP-ICP system for efficient vaporization of microliter samples and further quantitative analysis. The experimental parameters including ETV current, rf power and mass flow rate of argon carrier gas were optimized using the copper emission signal produced by 5 μl of standard solution (5 μg/ml). Under the optimized condition, the analytical performances including linearity, precision and detection limit for the developed system were investigated. Absolute detection limits in the range of 22–391 pg for selected eight elements (Fe, Cu, Cr, Mn, Pb, K, Zn and Mg) were obtained with satisfactory precision (<8.9% RSD). The feasibility of the developed system has been demonstrated by analyzing wheat gluten NIST standard sample.     

同位素稀释电感耦合等离子体质谱(ID-ICP-MS)测定植物与人发标准物质中的铅

建立了同位素稀释电感耦合等离子体质谱(ID-ICP-MS)测定铅的方法.考察和讨论了仪器参数对同位素比值测定的影响,优化了仪器的数据采样参数.利用内标Tl对质量歧视、系统漂移进行了校正.讨论了同位素浓缩剂加入量对最终浓度测定值的不确定度的影响.将该方法应用于植物标准物质和人发标准物质的测定,结果令人满意.     

Investigation of metal-binding metallothioneins in the tissues of rats after oral intake of cinnabar

The multi-metal-binding MT fractions in rat tissues after oral intake of cinnabar were characterized by hyphenated size-exclusion chromatography (SEC) and inductively coupled plasma mass spectrometry (ICP–MS). With the increase of both the feeding time and dosage of cinnabar the amounts of Hg-binding MT fractions in rat kidney of groups fed cinnabar increased significantly compared with the control group. Meanwhile, more Cu-binding MT were synthesized in the rat kidney, which confirmed the manipulating effect of MT in the homeostasis of Cu for detoxification of nephritic mercury. Although the Hg-binding MT fractions in rat liver of all cinnabar groups were almost independent of cinnabar dosage (2.5–5.0 g kg^–1 bw) and feeding time (2–4 weeks), the amount was much higher than that of the control group. The amounts of Hg-MT in other rat tissues of the cinnabar groups and the control group were compared and their significance is discussed.     

The use of carbon nanofibers microcolumn preconcentration for inductively coupled plasma mass spectrometry determination of Mn,Co and Ni

Based on carbon nanofibers (CNFs) as a solid phase extraction adsorbent, a microcolumn preconcentration method coupled to inductively coupled plasma mass spectrometry (ICP–MS) was developed for the determination of trace elements (Mn, Co and Ni). The effect of various experimental parameters such as pH, sample flow rate and volume, elution solution and interfering ions on the retention of the studied ions have been investigated systematically. During all the steps of the experimental process, Mn, Co and Ni could be quantitatively sorbed on the microcolumn containing CNFs in the range of pH 6.0–9.0, and then eluted completely with 0.5 mol ml^− 1 HNO₃. A preconcentration factor of 150-fold was obtained. The detection limits for Mn, Co and Ni were 40, 0.4 and 8.0 pg ml^− 1, respectively, with relative standard deviations less than 6.0%. In order to validate the proposed method, two certified reference materials of human hair (GBW 07601) and mussel (GBW 08571), and water sample were analyzed with satisfactory results. The recoveries were between 95.0 and 114%.     

Environmental Monitoring at Terra Nova Bay Station From 1989 to 1991

Abstract

Monitoring was carried on in the Italian Antarctic Station Terra Nova Bay. Airborne particulate matter was sampled at different Base locations during the Italian expeditions; samples were then analyzed at the ENEA laboratories for chemical characterization. The analyses were carried out by INAA (Instrumental Neutron Activation Analysis) for the determination of major, minor and trace elements (Na, K, Cs, Sc, V, Mn, Fe, Co, Zn, La) and by gas chromatography-mass spectrometry for the determination of PAH compounds. Data from the 1989–1990 and 1990–1991 campaigns are reported and discussed. Moreover, isokinetic samplings were carried out at the Base incinerator; the filters were analyzed by INAA; the V, Cr, Cu, Zn, Cd, Sb concentrations are reported.     

Time-based on-line preconcentration cold vapour generation procedure for ultra-trace mercury determination with inductively coupled plasma atomic emission spectrometry

A time-based sequential dispensing on-line column preconcentration procedure for mercury determination at trace levels by cold vapour generation inductively coupled plasma atomic emission spectrometry (CV-ICP-AES), by means of a unified module of a preconcentration column and a gas–liquid separator (PCGLS) is described. The complex of mercury formed on-line with ammonium pyrrolidine dithiocarbamate (APDC) is retained on the surface of the hydrophobic poly(tetrafluoroethylene) (PTFE) turnings, which are packed into the lower compartment of the PCGLS. Subsequently, mercury vapour is generated directly on the PTFE turnings by reductant SnCl₂ and separated from the liquid mixture via the PCGLS by argon purge gas. The outlet of the PCGLS is connected directly to the torch adapter of the plasma without the normal spray chamber and nebulizer. With 60-s preconcentration time and 12.0 mL min^–1 sample flow rate, the sampling frequency is 30 h^–1. The calibration curve is linear over the concentration range 0.02–5.0 g L^–1, the detection limit (c_L) is 0.01 g L^–1 and the relative standard deviation (s_r) is 3.1% at the 1.0 g L^–1 level. The proposed method was evaluated by analysis of BCR CRM 278 (Mytilus Edulis) reference material and applied to the determination of total mercury in digested urine, blood and hair samples.     

Determination of Trace Metals in Antarctic Sediments from Terra Nova Bay - Ross Sea

Abstract

Trace metals (Cu, Pb, Zn, Cd, Cr, Ni, Co, Mn) and iron concentration were determined in several sediments collected in the Antarctica (Terra Nova Bay—Ross Sea). Samples were analyzed by inductively coupled plasma (ICP-AES) after selective and total extraction. The results are in good agreement with the data previously collected in the same area.     

Determination of lead in bone tissues by axially viewed inductively coupled plasma multichannel-based emission spectrometry

A new procedure for determining low levels of lead in bone tissues has been developed. After wet acid digestion in a pressurized microwave-heated system, the solution was analyzed by inductively coupled plasma multichannel-based emission spectrometry. Internal standardization using the Co 228.615 nm reference line was chosen as the optimal method to compensate for the matrix effects from the presence of calcium and nitric acid at high concentration levels. The detection limit of the procedure was 0.11 g Pb g^–1 dry mass. Instrumental precision at the analytical concentration of ~10 g l^–1 ranged from 6.1 to 9.4%. Precision of the sample preparation step was 5.4%. The concentration of lead in SRM 1486 (1.32±0.04 g g^–1) found using the new procedure was in excellent agreement with the certified level (1.335±0.014 g g^–1). Finally, the method was applied to determine the lead in various fish bone tissues, and the analytical results were found to be in good agreement with those obtained through differential pulse anodic stripping voltammetry. The method is therefore suitable for the reliable determination of lead at concentration levels of below 1 g g^–1 in bone samples. Moreover, the multi-element capability of the technique allows us to simultaneously determine other major or trace elements in order to investigate inter-element correlation and to compute enrichment factors, making the proposed procedure particularly useful for investigating lead occurrence and pathways in fish bone tissues in order to find suitable biomarkers for the Antarctic marine environment.     

电感耦合等离子体原子发射光谱（ICP-AES）法测定粉煤灰中的铝

采用碳酸钠-碳酸钾-硼酸分解试样,盐酸浸取,电感耦合等离子体原子发射光谱法测定粉煤灰中的铝含量。铝的测定范围5.00%~25.00%。经加标回收实验,铝元素的加标回收率为99.6%~106%(n=3),方法准确简单,适用于粉煤灰中铝的测定。     

Determination of Trace Amounts of Cobalt in Blood

Abstract

The analysis of cobalt in whole blood and blood fractions has been carried out using three different analytical techniques namely, electrothermal atomic absorption spectrometry, inductively coupled plasma mass spectrometry and cathodic stripping voltammetry. This study showed that inductively coupled plasma mass spectrometry was the better equipped technique for conducting such analyses due to its low detection limits and wide linear dynamic range. The results ranged between 0.7 - 2.62 μg/l for plasma, 1.02 - 2.31 μg/l for serum, and 0.66 - 1.28 μg/l for whole blood. The introduction of different forms of cobalt to Wistar rats resulted in a differing distribution of the element between serum and whole blood. This observation suggests that there are at least two modes of Co uptake and transport depending on the administered or taken chemical form.     

Single-step microwave digestion with HNO(3) alone for determination of trace elements in coal by ICP spectrometry

A microwave digestion method with HNO₃ alone was conducted at a temperature as high as 250 °C for determination of 19 trace elements (Li, Be, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Cd, Cs, Ba, Hg, and Pb) in coal jointly by inductively coupled plasma optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS), and flow injection ICP-MS (FI-ICP-MS). The validity of determination was assessed by using three standard coals, SRM 1632c, BCR 180, and SARM 19. It was found that the high-temperature digestion led to an extensive decomposition of the organic matrix and clay in coal, and no dissolved and solid carbon remained in the final solution after evaporation. Good recoveries were observed for all trace elements in three coals, with the exception of V, Rb, and Cs in high-ash SARM 19. Additionally, FI-ICP-MS combined with the present digestion without evaporation pretreatment was proved to be a rapid and efficient approach for determination of ultra-trace elements such as Se, Cd, and Hg in coal.