Trace elemental analysis of automotive paints by laser ablation–inductively coupled plasma–mass spectrometry (LA–ICP–MS)

Paints and coatings are frequently encountered as types of materials that are submitted to forensic science laboratories as a result of trace evidence transfers. The aim of this study was to develop a method to complement the commonly used techniques in a forensic laboratory in order to better characterize these samples for forensic purposes. A laser ablation method has been used to simultaneously sample several layers directly prior to introduction into an inductively coupled plasma-mass spectrometer for the detection and quantification of the trace metals present in the layer(s). Time-resolved analysis plots displaying the elemental response and quantification of selected metals are compared to associate/discriminate paint samples. Matrix-matched standards were successfully incorporated into the analysis scheme for quantification of lead in the solid paint samples. Preparation of new matrix-matched standards for quantification of additional elements developed for this study are also presented. A sample set of eighteen (18) survey automotive paint samples have been analyzed with the developed method in order to determine the utility of LA-ICP-MS for trace element analysis of paints.     

Direct elemental analysis of biodiesel by inductively coupled plasma–mass spectrometry

An ICP–MS instrument fitted with an octopole reaction system (ORS) was used to directly measure the inorganic contents of several biofuel materials. Following sample preparation by simple dilution in kerosene, the biofuels were analysed directly. The ORS effectively removed matrix- and plasma-based spectral interferences to enable measurement of all important analytes, including sulfur, at levels below those possible by ICP–OES. A range of commonly produced biofuels was analysed, and spike recovery and long-term stability data was acquired. Suitably configured ICP–MS has been shown to be a fast and very sensitive technique for the elemental analysis of biofuels.     

Using inductively coupled plasma–mass spectrometry for calibration transfer between environmental CRMs

Multielement analyses of environmental reference materials have been performed using existing certified reference materials (CRMs) as calibration standards for inductively coupled plasma–mass spectrometry. The analyses have been performed using a high-performance methodology that results in comparison measurement uncertainties that are significantly less than the uncertainties of the certified values of the calibration CRM. Consequently, the determined values have uncertainties that are very nearly equivalent to the uncertainties of the calibration CRM. Several uses of this calibration transfer are proposed, including, re-certification measurements of replacement CRMs, establishing traceability of one CRM to another, and demonstrating the equivalence of two CRMs. RM 8704, a river sediment, was analyzed using SRM 2704, Buffalo River Sediment, as the calibration standard. SRM 1632c, Trace Elements in Bituminous Coal, which is a replacement for SRM 1632b, was analyzed using SRM 1632b as the standard. SRM 1635, Trace Elements in Subbituminous Coal, was also analyzed using SRM 1632b as the standard.     

Characterization of a sealed Americium–Beryllium (AmBe) source by inductively coupled plasma mass spectrometry

Two Americium–Beryllium neutron sources were dismantled, sampled (sub-sampled) and analyzed via inductively coupled plasma mass spectrometry (ICP-MS). Characteristics such as “age” since purification, actinide content, trace metal content and inter and intra source composition were determined. The “age” since purification of the two sources was determined to be 25.0 and 25.4 years, respectively. The systematic uncertainties in the “age” determination were ±4% 2σ. The amount and isotopic composition of U and Pu varied substantially between the sub-samples of Source 2 (n = 8). This may be due to the physical means of sub-sampling or the way the source was manufactured. Source 1 was much more consistent in terms of content and isotopic composition (n = 3 sub-samples). The Be–Am ratio varied greatly between the two sources. Source 1 had an Am–Be ratio of 6.3 ± 52% (1σ). Source 2 had an Am–Be ratio of 9.81 ± 3.5% (1σ). In addition, the trace element content between the samples varied greatly. Significant differences were determined between Sources 1 and 2 for Sc, Sr, Y, Zr, Mo, Ba and W.     

A simple method of target preparation for the bulk analysis of powder samples by laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS)

A simple and rapid procedure using a glue technique has been developed for the preparation of stable targets from powder samples for bulk analysis by LA– ICP–MS. The procedure was evaluated for the analysis of trace elements in SiC, of rare-earth elements in different types of silicate (rocks, sediments, and soils), and of Au and platinum-group elements in geological silicates. The test analysis was conducted using an IR laser in combination with a quadrupole mass spectrometer. The recommended preparation procedure offers the possibility of different types of calibration, for example application of certified reference samples in combination with prepared spiked samples on a base of a natural or synthetic matrix, or addition calibration. The resulting calibration functions are linear over a range of several decades. The trueness of the results was evaluated by use of certified reference samples. Analytical concentration ranges, detection limits, and the relative standard deviations are reported. Received: 20 November 2000 / Revised: 13 March 2001 / Accepted: 17 March 2001     

Geographic characterization of Greek wine by inductively coupled plasma–mass spectrometry macroelemental analysis

Abstract

Studying wine mineral profile has been proven as a valuable tool in geographical origin discrimination and authenticity for both producers and consumers. Adulteration of wines, in terms of geographical origin or variety, is considered a major topic of extensive research. Traceability and authenticity of wines have been previously studied on the basis of typical mineral element patterns by means of chemometric methods. In this context, analytical methods were developed for the determination of mineral elements in wines by inductively coupled plasma–mass spectrometry. This study aimed at classifying selected varietal Greek wines from various regions by employing instrumental analysis. Preliminary data of wine mineral content enabled for the classification of samples according to geographical origin and variety. However, further work is required in order to draw more valid conclusions and to obtain a detailed map of the mineral element content of Greek wines according to their geographical origin and/or variety.     

Determination of arsenic by inductively coupled plasma mass spectrometry – comparison of sample introduction techniques

A comparison is made of four sample introduction techniques for the determination of As by inductively coupled plasma mass spectrometry. The techniques studied were 1) flow injection with pneumatic nebulization (FIA-PN), 2) direct electrothermal vaporization (ETV), 3) continuous hydride generation (HG) and 4) hydride generation with in situ trapping followed by electrothermal vaporization (HG-ETV). It was found that FIA-PN and ETV gave similar detection limits in concentration units (about 20 pg mL^–1), although ETV had a much lower absolute detection limit (0.2 pg). Sample introduction by hydride generation gave an inferior detection limit (100–200 pg mL^–1), also in combination with in situ trapping and ETV, owing to the blank signal from traces of As in NaBH₄ which is difficult to eliminate. The results indicate that the more elaborate sample introduction techniques based on ETV and HG may not offer significant advantages compared to normal solution nebulization for the determination of As in simple sample matrices such as natural fresh waters, where matrix removal is not required.     

Use of pneumatic nebulization and laser ablation–inductively coupled plasma–mass spectrometry to study the distribution and bioavailability of an intraperitoneally administered Pt-containing chemotherapeutic drug

Quadrupole-based inductively coupled–mass spectrometry (ICP-MS) with pneumatic nebulization as a means of sample introduction was employed for quantification of platinum in blood and tissue samples of rats with peritoneal carcinomatosis, receiving intraperitoneal treatment with the Pt-containing chemotherapeutic drug oxaliplatin, and in the perfusate solution used for this purpose. The Pt levels were measured for various treatment conditions, i.e., with and without supporting treatment with the drug bevacizumab and at two different temperatures. Limits of detection obtained for platinum in blood and tissue samples were 0.3 and 2.0 pg g_,⁻¹ respectively. Evaluation of drug penetration into the tumor, under different conditions of treatment, was carried out via laser ablation–ICP-MS. Quantitative mapping of the Pt distribution in tissue sections of rat was attempted relying on gelatin standards. The results show an influence of the temperature at which the treatment is carried out, while supporting administration of the drug bevacizumab did not seem to affect the results.     

Mobile phase selection for the combined use of liquid chromatography–inductively coupled plasma mass spectrometry and electrospray ionisation mass spectrometry

Four different organic solvents: dimethylformamide, 1,4-dioxane, n-propanol and ethanol were evaluated as alternative organic modifiers to acetonitrile for liquid chromatography (LC) separations. The aim was to establish common sets of chromatographic conditions that could be applied for LC hyphenation to inductively coupled plasma mass spectrometry (ICPMS) as well as to electrospray ionization MS (ESIMS). The approach was to evaluate candidate solvents that, compared to acetonitrile, potentially could give improved analytical performance (low solvent vapor loading, maximized analyte sensitivity and minimized carbon depositions on instrumental parts) in ICPMS analysis while retaining chromatographic and ESIMS performances. The study showed that dimethylformamide, 1,4-dioxane, n-propanol and ethanol all can be advantageous chromatographic modifiers for LC–ICPMS analysis, giving superior performance compared to acetonitrile. For the combined use of LC–ICPMS and LC–ESIMS with a common set of chromatographic conditions, n-propanol gave the best overall performance. The ¹⁹⁵Pt⁺ signal in ICPMS was continuously monitored during a 0–60% organic solvent gradient and at 25% of organic modifier, 100% of the signal obtained at the gradient start was preserved for n-propanol compared to only 35% of the signal when using acetonitrile. Platinum detection limits were 5–8 times lower using n-propanol compared with acetonitrile. Signal-to-noise ratio in continuous ESIMS signal measurements was 100, 90 and 110 for a 100 μg/ml solution of leucine–enkephaline using acetonitrile, ethanol and n-propanol, respectively. Chromatographic efficiency in reversed phase separations was preserved for n-propanol compared to acetonitrile for the analysis of the whole protein cytochrome C and the peptide bacitracin on a column with particle and pore sizes of 5 μm and 300 Å, but slightly deteriorated for the separation of the peptides leucine–enkephaline and bacitracin on a 3 μm and 90 Å column as the peak width at half height for both peptides increased by a factor of two. The performance on the smaller dimensioned column could however be improved by running the separations at 40 °C.     

Depth profile analysis of various titanium based coatings on steel and tungsten carbide using laser ablation inductively coupled plasma –“time of flight” mass spectrometry

A homogenized 193 nm ArF* laser ablation system coupled to an inductively coupled plasma-”Time of Flight”-mass spectrometer (LA-ICP-TOFMS) was tested for depth profiling analysis on different single-layer Ti based coatings on steel and W carbides. Laser parameters, such as repetition rate, pulse energy and spatial resolution were tested to allow optimum depth related calibration curves. The ablation process using a laser repetition rate of 3 Hz, 120 μm crater diameter, and 100 mJ output energy, leads to linear calibration curves independent of the drill time or peak area used for calibrating the thickness of the layer. The best depth resolution obtained (without beam splitter) was 0.20 μm per laser shot. The time resolution of the ICP-TOFMS of 102 ms integration time per isotope was sufficient for the determination of the drill time of the laser through the coatings into the matrix with better than 2.6% RSD (about 7 μm coating thickness, n = 7). Variation of the volume of the ablation cell was not influencing the depth resolution, which suggests that the depth resolution is governed by the ablation process. However, the application on the Ti(N,C) based single layer shows the potential of LA-ICP-TOFMS as a complementary technique for fast depth determinations on various coatings in the low to medium μm region.     

Cerebral bioimaging of Cu, Fe, Zn, and Mn in the MPTP mouse model of Parkinson’s disease using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS)

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been established as a powerful technique for the determination of metal and nonmetal distributions within biological systems with high sensitivity. An imaging LA-ICP-MS technique for Fe, Cu, Zn, and Mn was developed to produce large series of quantitative element maps in native brain sections of mice subchronically intoxicated with 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridin (MPTP) as a model of Parkinson’s disease. Images were calibrated using matrix-matched laboratory standards. A software solution allowing a precise delineation of anatomical structures was implemented. Coronal brain sections were analyzed crossing the striatum and the substantia nigra, respectively. Animals sacrificed 2 h, 7 d, or 28 d after the last MPTP injection and controls were investigated.     

β-Cyclodextrin-cross-linked polymer as solid phase extraction material coupled with inductively coupled plasma mass spectrometry for the analysis of trace Co(II)

A sensitive method for the separation/analysis of Co(II) was described. The β-cyclodextrin cross-linked polymer (β-CDCP) was synthesized and used as solid phase extraction material (SPE) to separate/pre-concentrate trace cobalt coupled with inductively coupled plasma mass spectrometry (ICP-MS) for the analysis of Co(II). The method was based on α-pyridylazo-β-naphthol (PAN) as the complexing agent for Co(II)-PAN at neutral condition and the adsorption behavior of Co(II)-PAN on β-CDCP was studied. Further, p-octylpolyethylene-glycolphenyl ether (Triton X-100) as environment-friendly eluant was used. The linear range, detection limit (DL) and the relative standard deviation (R.S.D.) was 5.0-160.0 ng/mL, 5.84 ng/L and 2.27% (n = 3, c = 30.0 ng/mL) respectively. The enhancement factor was 10. Moreover, the β-CDCP could be used repeatedly and offered better recovery and estimation of standard samples.     

Were Chinchorros exposed to arsenic? Arsenic determination in Chinchorro mummies' hair by laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS)

Chinchorros, a fishermen culture, who lived about 7000 years ago in the coastal region of the Atacama Desert in the northern outpost of present-day Chile, practiced an intricate system of mummification of their dead. The drinking water in this region is rich with arsenic, and the mummies were found in these arsenic endemic areas. Well preserved mummy hair samples provided a unique opportunity to explore the ancient arsenic exposure of the Chinchorros by laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) using a single hair strand without any elaborate sample preparation. Forty-six hair samples from mummies found in five burial sites around the Atacama Desert, Chile, were used for this study. After cleaning, hair strands were placed on mounting tape and ablated using a Nd-YAG UV laser coupled to ICP-MS. A suite of contemporary human hair from the same region with known arsenic concentrations was used for calibration of LA-ICP-MS. Satisfactory linear calibration functions were obtained for arsenic in hair. The method detection limit was 0.8 µg/g and the sample throughput for this method is ∼ 10 samples per hour. It appears that mummies from the Morro (Arica), Iquique and Camarones had the elevated concentration of arsenic in hair (AsH > 10 µg/g) in this sub-set of samples, where Morro had the broad distribution of As concentrations.     

Analysis of Ir in Köfelsit rocks by inductively coupled plasma–sector-field mass spectrometry (ICP–SFMS)

Three different analytical strategies have been evaluated for the quantification of Ir in geological samples. Glassy rock samples from Köfels and reference material WGB-1 were analyzed directly by inductively coupled plasma sector field mass spectrometry (ICP–SFMS) at mass resolution 400 using membrane desolvation and at mass resolution 9500 without membrane desolvation. Matrix separation by anion-exchange pre-concentration was also investigated. The ultrasonic nebulizer USN6000AT⁺ (Cetac Technologies, Omaha, NE, USA) incorporating a membrane desolvation unit was used as the sample-introduction system. Sample preparation involved complete microwave-assisted acid digestion of the silicate matrix with HNO₃–HCl–HF. The results obtained by the three methods of quantification were in good agreement, showing that oxide-type interferences were effectively eliminated solely by membrane desolvation. The limits of detection were 6 pg g^–1 for low resolution measurement with use of the membrane, 15 pg g^–1 at a mass resolution of 9500, and 59 pg g^–1 for the ion-exchange procedure. The ultimate precision obtained for the Köfelsit Ir data was, however, compromised by the small sample intake (0.3 g), because of the inhomogeneous distribution of Ir in geological samples.     

Rapid and simple determination of selenium in blood serum by inductively coupled plasma–mass spectrometry (ICP–MS)

An inductively coupled plasma mass spectrometer (ICP-MS) with a rapid sample-preparative procedure was used for the determination of selenium in blood serum. Blood serum was prepared by dilution in an acidic solution consisting of nitric acid (1%), X-triton (0.1%) and 1-butanol (0.8%). A calibration curve was established for 1-40 microg mL(-1) (r(2)>0.99). The limit of detection was 0.5 microg mL(-1). Repeatability and intermediate precision were satisfactory with relative standard deviations (RSD) of 2.0% and 3.2%, respectively. This method was easily applied to reference materials with satisfactory accuracy. Good correlation (r(2)=0.96) was observed between ICP-MS and atomic absorption spectrometry (AAS) for the determination of (82)Se in blood serum from 23 patients. These results suggest that the sample preparative procedure coupled with ICP-MS can be used for the routine determination of (82)Se in human blood serum.     

Evaluation of measurement uncertainty in the elemental analysis of sintered silicon carbide using laser ablation in liquid—inductively coupled plasma mass spectrometry with external calibration and isotope dilution

Accreditation and Quality Assurance - The goal of this study was to evaluate the uncertainty of elemental analytical methods that use laser ablation in liquid (LAL) as a pretreatment. After LAL...     

Characterization and quantification of metallothionein isoforms by capillary electrophoresis–inductively coupled plasma–isotope-dilution mass spectrometry

In a new approach to the characterization and quantification of metallothionein isoforms an on-line isotope-dilution method in combination with the coupling of capillary electrophoresis (CE) to an inductively coupled plasma-sector field mass spectrometer (ICP-SFMS) is reported. Metallothionein (MT) isoforms are separated by CE and the elements Cu, Zn, Cd, and S are detected simultaneously by use of ICP-SFMS in the medium resolution mode. On-line isotope dilution is performed by continuous introduction of an isotopically enriched, species-unspecific spike solution after the separation step. MT from rabbit liver and a further purified MT-1 isoform were quantified by determination of sulfur, and the stoichiometric compositions of the metalloprotein complexes are characterized by determination of their sulfur-to-metal ratios.     

Determination of macro and trace elements in canned marine products by inductively coupled plasma—optical emission spectrometry (ICP-OES) and ICP—mass spectrometry (ICP-MS)

This study determined the concentration of eight macroelements (Na, K, Mg, P, S, Ca, Fe, Zn) and nineteen trace elements (Li, Be, Cr, Mn, Co, Ni, V, Cu, Ga, Se, Rb, Sr, In, Sn, Cs, Ba, Tl, Bi, U) in commonly consumed canned marine products from South Korea. The samples were wet-digested using nitric acid and hydrogen peroxide by a microwave system and analyzed for macroelements using inductively coupled plasma—optical emission spectrometry (ICP-OES) and for trace elements by inductively coupled plasma—mass spectrometry (ICP-MS). The analytical methods were validated by the correlation coefficients, limits of detection and quantification, correlation variance, spiking recovery tests, and analyzing a NIST 1566?b oyster tissue certified reference material. The concentrations of macro and trace elements varied among the canned marine products. The macroelements were present in the order of Na?>?K?>?P?>?S> Mg?>?Ca?>?Fe?>?Zn. In general, the concentrations of macro and trace elements were within the specified limits of Food and Nutrition Board, Joint Food and Agriculture Organization/World Health Organization Expert Committee on Food Additives, and Ministry of Food and Drug Safety, Korea. The results suggest that the analyzed canned marine products are safe in terms of the analyzed elements and their consumption therefore does not cause any threat to human health.     

Ultra-sensitive quantification of lysozyme based on element chelate labeling and capillary electrophoresis–inductively coupled plasma mass spectrometry

In this study, an ultra-sensitive method for the quantification of lysozyme based on the Gd³⁺ diethylenetriamine-N,N,N′,N″,N″-pentaacetic acid labeling and capillary electrophoresis–inductively coupled plasma mass spectrometry (CE–ICP–MS) was described. The Gd³⁺-tagged lysozyme was effectively separated by capillary electrophoresis (CE) and sensitively determined by inductively coupled plasma mass spectrometry (ICP–MS). Based on the gadolinium-tagging and CE–ICP–MS, the lysozyme was determined within 12 min with an extremely low detection limit of 3.89 attomole (3.89 × 10⁻¹¹ mol L⁻¹ for 100 nL of sample injection) and a RSD < 6% (n = 5). The proposed method has been successfully used to detect lysozyme in saliva samples with a recovery of 91–106%, suggesting that our method is sensitive and reliable. The success of the present method provides a new potential for the biological assays and sensitive detection of low-abundant proteins.