In-situ micro-analysis of platinum and rare earths in ferromanganese crusts by laser ablation-ICP-MS (LAICPMS)

A 500 mJ Nd: YAG laser coupled to an inductively coupled plasma mass spectrometer (ICPMS) has been used for the direct determination of platinum (Pt) and the rare earth elements (REE) in concentration micro-profiles through ferromanganese crusts from the South Pacific. The instrument has been calibrated with briquetted powder pellets of U.S.G.S. reference materials NOD-A-1 and NOD-P-1. Linear calibration curves including the origin have been obtained for all elements of interest. An external calibration strategy has been developed which also accounted for variations in instrument response. The precision of the LA-ICP-MS measurements in this matrix has been 4–5% for platinum and <4% for the rare earths. Platinum concentrations have varied from 150 ng g^–1 to 500 ng g^–1 through the analysed microprofile. Two major peak areas in the platinum concentration profile have correlated roughly with cerium values and with changes in the normalised REE pattern: an enrichment of Pt coincides with a pronounced positive cerium anomaly and with an enrichment of the heavy REE relative to the light REE.     

Characteristics of Size-Fractionated Urban Aerosols and Trace Gases in Budapest

An air pollution study was conducted at two urban residential sites in Budapest from 9 April to 17 May 1996. Size-fractionated aerosol samples were simultaneously collected on a daily basis, and meteorological conditions were recorded at both sampling sites. Stacked filter units (SFUs) with an upper size inlet cutoff were used as sampling devices separating the urban aerosol into coarse [about 2- to 10-μm equivalent aerodynamic diameter (EAD)] and fine (<2 μm EAD) size fractions. In addition, atmospheric concentrations of some criteria pollutants, i.e., NO, NO₂, SO₂, CO, and total mass of the suspended particulate matter (TSP) were measured every half-hour at one of the sampling sites with commercial equipment. The SFU filters were weighed and analyzed by a light reflectance technique, particle-induced X-ray emission analysis, and instrumental neutron activation analysis. Atmospheric concentrations for 31 aerosol species have been obtained so far. The analytical results were used to characterize the levels and the multielemental composition of the urban aerosol at both sampling sites and for both size fractions, to investigate the atmospheric concentrations and diurnal variation of the criteria pollutants, and to compare the time trends of aerosols and trace gases. The present paper reports on the status of the air pollution study and gives a discussion of the results.     

Laser ablation inductively coupled plasma mass spectrometry for imaging of copper, zinc, and platinum in thin sections of a kidney from a mouse treated with cis-platin

Platinum complexes are used for the treatment of several types of cancer. High platinum concentrations in the target tissue and low concentrations in dose-limiting tissue structures such as renal tubules are desirable to assure selective toxicity. Microlocal analysis of platinum distribution in tissue sections may thus contribute to the optimization of platinum therapy. Scanning laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to produce images of element distribution in 14-μm thin sections of kidney tissue from a mouse treated with cis-platin 60 min prior to victimization. The sample surface was scanned (raster area 300 mm²) with a focused laser beam (wavelength 266 nm, diameter of laser crater 50 μm, inter line distance 50 μm and laser power density 3 × 10⁹ W cm⁻²) in a cooled laser ablation chamber (about −15 °C) developed for these measurements. The laser ablation system was coupled to a double-focusing sector field ICP-MS. Ion intensities of ⁶³Cu⁺, ⁶⁴Zn⁺, and ¹⁹⁶Pt⁺ were measured within the tissue by LA-ICP-MS. Matrix-matched laboratory standards served for calibration of analytical data. The mass spectrometric analysis yielded an inhomogeneous distribution for Cu, Zn, and Pt in thin kidney sections. Copper was enriched in the capsule and outer cortex, zinc in the inner cortex and the platinum concentration followed a centripetal gradient with clear medullar enrichment. Thus, scanning LA-ICP-MS may be a useful tool in the preclinical development of new and less nephrotoxic platinum complexes.     

电感耦合等离子体-质谱联用及其在环境和生物样品中铂族金属分析的应用进展

本文简述了电感耦合等离子体-质谱联用(LCP-MS)技术和仪器的发展,分析了环境和生物样品中铂族金属分析的主要困难,综述了90年代以来国内外ICP-MS技术在环境和生物样品中铂族金属分析的最新进展,引用文献47篇.     

Determination of B in body fluids by isotope dilution inductively coupled mass spectrometry with direct injection nebulization

The determination of B in small volumes of undigested blood plasma and urine by isotope dilution and high efficiency direct injection nebulization (DIN) inductively coupled plasma mass spectrometry (ICP-MS) is proposed. The C interference over ¹¹B was removed by precipitating the samples proteins. Samples aliquots of 1 ml were spiked with an enriched ¹⁰B solution and shaken during 1 h to attain the isotopic equilibrium. Thereafter, the sample proteins were denaturated with nitric acid and the supernatant was analyzed. This procedure was effective to reduce C concentrations in approximately 94%. Sample volumes of 50 μl were introduced into the ICP by the direct injection nebulizer producing transient signals lasting 30 s for B isotopes measurements. Precision of ¹⁰B/¹¹B measurements was characterized by relative standard deviation (RSD) lower than 1%. The instrumental mass discrimination factor was lower than 5%. Total B concentrations from 100 to 135 μg L⁻¹ in plasma and 0.499 to 3.021 mg L⁻¹ in urine samples were found. Reproducibility of triplicate samples was characterized by RSD<2.0% for plasma and lower than 1.3% for urine samples. Limit of detection (3σ) of 0.6 ng ml⁻¹ was calculated from synthetic blood plasma blank. Results of the denatured supernatant and digested plasma and urine samples were comparable at the 95% confidence level.     

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.     

Determination of Molybdenum and Vanadium in Seawater by Ion-Exchange Preconcentration-Inductively Coupled Plasma Atomic Emission Spectrometry

A simple and rapid method has been developed for the determination of molybdenum and vanadium in seawater using ion-exchange preconcentration and inductively coupled plasma atomic emission spectrometry (ICP-AES). One hundred milliliters of seawater prepared as 0.05 M hydrochloric acid solution is passed through a cellulose phosphate column, and molybdenum and vanadium adsorbed on the cellulose are eluted simultaneously with dilute ammonia solution. The effluent collected is evaporated to a small volume, in which molybdenum and vanadium can be determined by ICP-AES. The overall recoveries of molybdenum and vanadium are 93.6 and 80.4%, respectively, at the level of 1 μgMo/100 ml and 0.1 μgV/100 ml. The proposed method has been successfully applied to the determination of the two elements in several seawater samples. Relative standard deviations (n = 3) are 2.0-2.9 and 0.3-4.3% for molybdenum and vanadium, respectively.     

Determination of long-lived radionuclides in concrete matrix by laser ablation inductively coupled plasma mass spectrometry

A laser ablation system using a Nd:YAG laser was coupled both to a quadrupole inductively coupled plasma (ICP) mass spectrometer and to a double-focusing sector field ICP mass spectrometer. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was applied for the determination of long-lived radionuclides in a concrete matrix. The investigated samples were two laboratory standards with a concrete matrix, which we doped with different long-lived radionuclides (e.g. ⁹⁹Tc, ²³²Th, ²³³U, ²³⁷Np) from the ng g⁻¹ to μ g⁻¹ concentration range and an undoped concrete material (blank). Detection limits for long-lived radionuclides in the 10 ng g⁻¹ range are reached for LA-ICP-MS using the quadrupole mass spectrometer. With double-focusing sector field ICP-MS, the limits of detection are in general one order of magnitude lower and reach the sub ng g⁻¹ range for ²³³U and ²³⁷Np. A comparison of mass spectrometric results with those of neutron activation analysis on undoped concrete sample indicates that a semiquantitative determination of the concentrations of the minor and trace elements in the concrete matrix is possible with LA-ICP-MS without using a standard reference material.     

Application of laser ablation ICP-MS to elemental analysis of glasses

A technique involving the coupling of laser ablation and inductively coupled plasma mass spectrometer has been used for semi-quantitative analysis of glasses without sample dissolution. The characteristic features of this technique is low detection limit and accuracy between a few % up to 20%. An NIST glass standard (SRM 612) was dissolved and then analysed by ICP-MS in semi-quantitative mode. The results were in close agreement with the certified values for elements such as Mn, Sr, Y, Ti...Abbreviations AA atomic absorption - ICP-OES inductively coupled plasma optical emission spectroscopy - ICP-MS inductively coupled plasma mass spectrometry - LA laser ablation     

Estimation of platinum in environmental water samples with solid phase extraction technique using inductively coupled plasma mass spectrometry

A solid phase extraction technique for the determination of platinum(IV) at trace levels by inductively coupled plasma mass spectromA solid phase extraction technique for the determination of platinum(IV) at trace levels by inductively coupled plasma mass spectrometry (ICP-MS) was developed. The method was based on retention of platinum in a sample on silica gel modified with aminepropyl groups. The retention of platinum(IV) from the sample solution and the recovery of platinum with 1.0 mol L⁻¹ thiourea solution were quantitative. The relative standard deviation (RSD) was calculated as 5% (n = 7) at the 10 ng L⁻¹ level. The enrichment factor was found to be (50-fold) for 250 mL of water sample. Under optimum conditions, the method detection limit (MDL) was found to be 1 ng L⁻¹ for platinum in water matrices. Recoveries of Pt from spike addition to atmospheric water samples were quantitative (80–95%). The present method was used for the determination of platinum in precipitation, throughfall and runoff water samples.      

ICP-MS determination of Pt in biological fluids of patients treated with antitumor agents: evaluation of analytical uncertainty

The estimation of the uncertainty associated to the analytical methods is necessary in order to establish the comparability of results. Methods of Pt determination in biological fluids lack very often of information about uncertainty of results, with likely implications when results are used to interpret the mechanism of action of platinum compound or when they are considered to optimise the clinical therapies.An inductively coupled plasma-mass spectrometer (ICP-MS) method for the determination of Pt in biological fluids (plasma, ultrafiltrate and urine) of patients treated with antitumor agents has been developed and validated. The limits of quantification (LOQ) in the three matrices were 1.0, 0.1, and 2.0 μg/l, respectively.Intraday and interday precisions and accuracies were in good agreement with the FDA criteria for the validation of analytical methods. The validation study was implemented by assessing the uncertainty evaluation for Pt determination in the different matrices according to EURACHEM/CITAC Guide.     

Speciation of halogenides and oxyhalogens by ion chromatography-inductively coupled plasma mass spectrometry

A speciation method utilizing ion chromatography coupled with inductively coupled plasma mass spectrometry is described for simultaneous analysis of eight halogenides and oxyhalogens: chloride, chlorite, chlorate, perchlorate, bromide, bromate, iodide and iodate. The method was applied for the analysis of drinking water samples collected from water treatment plants in areas in Finland, which are known to have high bromine concentrations in ground water. Water samples collected before and after disinfection were analyzed to get information about potential species conversion as a result of purification. Chloride and chlorate were the chlorine species found in these water samples, and iodine existed as both iodate and iodide. In the case of bromine, species conversion had taken place, since total bromine concentrations were increased during disinfection but bromide concentrations were decreased. No bromate was observed in the samples. The detection limits for all the chlorine species studied were 500 μg/l, for bromine species studied 10 μg/l, for iodide 0.1 μg/l and for iodate 0.2 μg/l.     

Natural sources and heavy metals

PTS, PM10 and PM2.5 samples have been collected at a rural site of south-east Italy (40 degrees 20' 13" N; 18 degrees 6' 47" E) from June to October, 2004 to investigate natural and anthropogenic contributions on particulate matter and heavy metal mass concentrations. It is shown that sharp-peak particulate-matter concentrations have been recorded during most African dust outbreaks occurred over south-east Italy. In particular, PM10 concentrations exceeding the 24-hour limit value of 50 microg/m3 have been monitored during dust events. Al, Cd, Cr, Cu, Fe, Mn, V, Ni, Pb, and Zn metal concentrations have been evaluated by an inductively coupled plasma atomic emission spectrometer and Al mass concentrations >500 ng/m3 have been observed in PTS and PM10 samples during the advection of African dust particles. Accordingly to geochemical calculations Al, Fe, and Mn, have a significant crustal origin while, Cd, Cu, Pb, and Zn are of anthropogenic origin. Moreover, Fe resulted predominant in the coarse particle fraction, while Ni, Pb, V, and Zn were predominant in the fine particle fraction. It is also shown that Cd, Mn, Ni, Pb, and V concentrations never exceeded guide and/or limit values recommended by the World Health Organization and the European Council Directives.     

Fractionation of metals and metalloids by chemical bonding from particles accumulated by electrostatic precipitation in an Argentine thermal power plant

A study was undertaken to evaluate the distribution of Al, As, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn in fly ashes collected in the electrostatic precipitator of a thermal power plant in San Nicolás (Argentina). Five samples were collected during one week of operation. For the fractionation, the scheme applied consisted in extracting the elements in four fractions namely (i) soluble and exchangeable elements; (ii) carbonates, oxides and reducible elements; (iii) bound to sulfidic metals; and (iv) residual elements. Metals and metalloids at μg g^− 1 level were determined in each fraction by inductively coupled plasma optical emission spectrometry (ICP OES). For validation, a standard reference material (SRM 1633 coal fly ash) from NIST was subjected to the same chemical sequential extraction procedure that the samples. X-ray diffraction powder (XRD) analysis and scanning electron microscopy (SEM) were used to characterize the major minerals present in the matrix. Total analyte concentration (in μg g^− 1) varied from 10.6 for Pb to 17,622 for Al. Minimum and maximum concentrations (in μg g^− 1) found in individual samples in the four fractions were: Al, 92.7–9668; As, < 0.3–143; Cr, 2.0–10.4; Cu, < 0.2–35.6; Fe, < 0.3–4992; Mn, < 0.1–128; Ni, < 0.3–139; Pb, < 0.5–9.1; Ti, < 0.3–2243; V, 17.0–112.9; and Zn, < 0.1–68.2. The leachability of the 11 elements under study proved to be different. Low percentages of Al (1%), V (7%) and Cr (8%) were detected in the most bioavailable fraction. Arsenic was found to be most abundant in the non-silicate phase, represented by the second and third fractions, while Cr, Fe, Ni, Pb and Zn were mostly associated to the residual fraction.     

Incidence of Fusarium Mycotoxins in Wheat and Maize from Albania

In this study, ten Fusarium toxins were analysed in wheat and maize commodities from Albania. In total, 71 samples of wheat and 45 samples of maize were collected from different producing regions. The analytical procedure consisted of a simple one-step sample extraction followed by the determination of toxins using liquid chromatography coupled with tandem mass spectrometry. Fusarium toxins were found in 23% of the analysed wheat samples and in 78% of maize samples. In maize samples, most often fumonisins B₁ (FB1) and B₂ (FB2) were found. They were present in 76% of samples. They were detected in all positive samples except in one with concentrations ranging from 59.9 to 16,970 μg/kg. The sum of FB1 and FB2 exceeded the EU maximum permitted level (4000 μg/kg) in 31% of maize samples. In wheat samples, the only detected Fusarium mycotoxin was deoxynivalenol (DON), present in 23% of samples. In one sample with the concentration of 1916 μg/kg, the EU maximum permitted level (1250 μg/kg) was exceeded. This is the first report on the presence of Fusarium toxins in wheat and maize grains cultivated in Albania.     

Chemical characterization of airborne particulate matter in ambient air of Nagoya, Japan, as studied by the multielement determination with ICP-AES and ICP-MS.

The multielement determination of PM(10) (airborne particulate matter smaller than 10 microm) samples, which was collected by a high volume air sampler at the urban site of Nagoya City, was carried out by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The present analytical method was validated by analyzing urban particulate matter standard reference material of NIST SRM 1648. The analytical data for ca. 30 elements in PM(10) samples collected during a period from 8 September to 9 October, 2003, were obtained in the concentration range from sub-microg g(-1) to several-10 mg g(-1), but the data for 18 elements among ca. 30 elements were available for the characterization of PM(10) samples in ambient air, because of problems caused by the filter blanks. Then, the trends concerning the distributions of diverse elements in PM(10) samples were analyzed based on the enrichment factors and size distribution factors. The lithophile and siderophile elements were distributed more than 50% in coarse particle fraction (>2.1 microm), which was derived mainly from natural sources, such as soils and crustal minerals. On the other hand, chalcophile elements were distributed more than 50% in fine particle fraction (<2.1 microm), which was derived mostly from anthropogenic emission sources. The large enrichment of chalcophile elements in PM(10) samples as well as their mining influence factors (MIFs) suggested their wide use in industrial productions.     

电感耦合等离子体质谱(ICP-MS)及其联用技术研究进展

综述了电感耦合等离子体质谱(ICP-MS)及其联用技术的研究进展,详细阐述了:1)各种色谱与ICP-MS的接口研究;2)MS技术的改进及信息处理研究,如采用碰撞池技术,高分辨等离子体质谱仪、多接收高分辨等离子体质谱仪和飞行时间质谱仪等;3)进样技术和联用技术,如激光烧蚀、微波消解、冷蒸发进样等技术的进展。讨论了电感耦合等离子体质谱及联用技术的发展趋势,并对目前存在的主要问题及可能的解决方案进行了讨论。     

Determination of cadmium in oyster tissue using isotope dilution inductively coupled plasma mass spectrometry: comparison of results obtained in the standard and He/H2 cell modes

An inductively coupled plasma quadrupole mass spectrometer equipped with an octopole collision/reaction cell was used for the determination of cadmium in oyster tissue samples using isotope dilution inductively coupled plasma mass spectrometry. The oyster samples in question were found to contain Mo and Zr. In our feasibility study on a Cd standard solution (10 μg L⁻¹) containing a matrix of Mo (1000 μg L⁻¹) or Zr (250 μg L⁻¹), the potentially interfering species (MoO⁺ or ZrO⁺) present at the analytical mass of cadmium concerned (m/z 111, 112 or 114) was reduced effectively through the use of a mixture of He and H₂ as cell gases. The accuracy of the method was validated by the analysis of a matrix-matched certified reference material (CRM) of NIST SRM 1566b. The CRM was analyzed under the standard and He/H₂ cell modes. Two isotopic pairs of ¹¹⁴Cd/¹¹¹Cd and ¹¹²Cd/¹¹¹Cd were selected for quantification purposes. The recoveries of cadmium obtained in the two cell modes were compared with each other. The validated method was applied successfully to the APMP.QM-P5 pilot study for international comparability purposes.     

Dissolution of Platinum Single Crystals in Acidic Medium

Platinum single crystal basal planes consisting of Pt(111), Pt(100), Pt(110) and reference polycrystalline platinum Pt(poly) were subjected to various potentiodynamic and potentiostatic electrochemical treatments in 0.1 M HClO₄. Using the scanning flow cell coupled to an inductively coupled plasma mass spectrometer (SFC-ICP-MS) the transient dissolution was detected on-line. Clear trends in dissolution onset potentials and quantities emerged which can be related to the differences in the crystal plane surface structure energies and coordination. Pt(111) is observed to have a higher dissolution onset potential while the generalized trend in dissolution rates and quantities was found to be Pt(110)>P(100)≈Pt(poly)>Pt(111).     

Method Validation for Determination of Thallium by Inductively Coupled Plasma Mass Spectrometry and Monitoring of Various Foods in South Korea

Thallium (Tl) is a rare element and one of the most harmful metals. This study validated an analytical method for determining Tl in foods by inductively coupled plasma mass spectrometry (ICP-MS) based on food matrices and calories. For six representative foods, the method’s correlation coefficient (R²) was above 0.999, and the method limit of detection (MLOD) was 0.0070–0.0498 μg kg⁻¹, with accuracy ranging from 82.06% to 119.81% and precision within 10%. We investigated 304 various foods in the South Korean market, including agricultural, fishery, livestock, and processed foods. Tl above the MLOD level was detected in 148 samples and was less than 10 μg kg⁻¹ in 98% of the samples. Comparing the Tl concentrations among food groups revealed that fisheries and animal products had higher Tl contents than cereals and vegetables. Tl exposure via food intake did not exceed the health guidance level.