Multielement analysis of polyethylene using solid sampling electrothermal vaporization ICP mass spectrometry

Next to laser ablation (LA) also electrothermal vaporization (ETV) from a graphite furnace as a means of sample introduction opens possibilities for direct analysis of solid samples using inductively coupled plasma mass spectrometry (ICPMS). In this paper, it is demonstrated that solid sampling ETV-ICPMS is very well suited for the determination of metal traces in polyethylene. A limited multielement capability is often cited as an important drawback of ETV-ICPMS. However, by studying the effect of monitoring an increasing number of mass-to-charge ratios on the signal profile (integrated signal intensity and repeatability) of selected analyte elements, the multielement capability of (solid sampling) ETV-ICPMS was systematically evaluated, and the results obtained suggest that, with a quadrupole-based ICPMS instrument, at least 11 elements can be determined "simultaneously" (from the same vaporization step), in essence without compromising the sensitivity or the precision of the results obtained. In this work, the "simultaneous" determination of Al, Ba, Cd, Cu, Mn, Pb, and Ti in a polyethylene candidate reference material has been accomplished, despite the large variation in analyte concentration (from 5 ng/g for Mn to 500 microg/g for Ti) and in furnace behavior (volatility) they exhibit. To avoid premature losses of Cd during thermal pretreatment of the samples, Pd was used as a chemical modifier. Two different calibration methods--external calibration using an aqueous standard solution and single standard addition--were studied and the results obtained were compared with those obtained using neutron activation analysis (NAA) and/or with the corresponding (candidate) certified values (if available). Single standard addition was shown to be preferable (average deviation between ICPMS result and reference value < 3%), although--except for Ba--acceptable results could also be obtained with external calibration.     

Imaging of copper, zinc, and other elements in thin section of human brain samples (hippocampus) by laser ablation inductively coupled plasma mass spectrometry

Laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) was used to produce images of element distribution in 20-microm thin sections of human brain tissue. The sample surface was scanned (raster area approximately 80 mm(2)) with a focused laser beam (wavelength 213 nm, diameter of laser crater 50 microm, and laser power density 3 x 10(9) W cm(-2)) in a cooled laser ablation chamber developed for these measurements. The laser ablation system was coupled to a double-focusing sector field ICPMS. Ion intensities of 31P+, 32S+, 56Fe+, 63Cu+, 64Zn+, 232Th+, and 238U+ were measured within the area of interest of the human brain tissue (hippocampus) by LA-ICPMS. The quantitative determination of copper, zinc, uranium, and thorium distribution in thin slices of the human hippocampus was performed using matrix-matched laboratory standards. In addition, a new arrangement in solution-based calibration using a micronebulizer, which was inserted directly into the laser ablation chamber, was applied for validation of synthetic laboratory standard. The mass spectrometric analysis yielded an inhomogeneous distribution (layered structure) for P, S, Cu, and Zn in thin brain sections of the hippocampus. In contrast, Th and U are more homogeneously distributed at a low-concentration level with detection limits in the low-nanogram per gram range. The unique analytical capability and the limits of LA-ICPMS will be demonstrated for the imaging of element distribution in thin cross sections of brain tissue from the hippocampus. LA-ICPMS provides new information on the spatial element distribution of the layered structure in thin sections of brain tissues from the hippocampus.     

Diode laser thermal vaporization inductively coupled plasma mass spectrometry

An approach of sample introduction for inductively coupled mass spectrometry (ICPMS), diode laser thermal vaporization (DLTV) is described. The method allows quantitative determination of metals in submicroliter volumes of liquid samples. Laser power is sufficient to induce pyrolysis of a suitable substrate with the deposited sample leading to aerosol generation. Unlike existing sample introduction systems based on laser ablation, it uses a NIR diode laser rather than an expensive high-energy pulsed laser. For certain elements, this sample introduction technique may serve as an alternative to solution analysis with conventional nebulizers. Using a prearranged calibration set, DLTV ICPMS provides rapid and reproducible sample analysis (RSD ~ 10%). Sample preparation is fast and simple, and the prepared samples can easily be archived and transported. The limits of detection for Co, Ni, Zn, Mo, Cd, Sn, and Pb deposited on the preprinted paper were found to be in the range of 0.4-30 pg. The method was characterized, optimized, and applied to the determination of Co in a drug preparation, Pb in whole blood, and Sn in food samples without any sample pretreatment.     

Comparison of ultraviolet femtosecond and nanosecond laser ablation inductively coupled plasma mass spectrometry analysis in glass, monazite, and zircon

We compared the analytical performance of ultraviolet femtosecond and nanosecond laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). The benefit of ultrafast lasers was evaluated regarding thermal-induced chemical fractionation, that is otherwise well known to limit LA-ICPMS. Both lasers had a Gaussian beam energy profile and were tested using the same ablation system and ICPMS analyzer. Resulting crater morphologies and analytical signals showed more straightforward femtosecond laser ablation processes, with minimal thermal effects. Despite a less stable energy output, the ultrafast laser yielded elemental (Pb/U, Pb/Th) and Pb isotopic ratios that were more precise, repeatable, and accurate, even when compared to the best analytical conditions for the nanosecond laser. Measurements on NIST glasses, monazites, and zircon also showed that femtosecond LA-ICPMS calibration was less matrix-matched dependent and therefore more versatile.     

Determination of phosphorus-, copper-, and zinc-containing human brain proteins by LA-ICPMS and MALDI-FTICR-MS

Human brain proteins containing phosphorus, copper, and zinc were detected directly in protein spots in gels of a human brain sample after separation by two-dimensional gel electrophoresis using laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). A powerful laser ablation system with cooled laser ablation chamber was coupled to a double-focusing sector field ICPMS. The separated protein spots in 2D gels were fast screened using the optimized microanalytical LA-ICPMS technique measured at medium mass resolution with a focused laser beam (wavelength, 213 nm; diameter of laser crater, 50 mum; and laser power density, 3 x 10(9) W cm(-2)) with respect to selected three essential elements. Of 176 protein spots in 2D gel from a human brain sample, phosphorus, copper, and zinc were detected in 31, 43, and 49 protein spots, respectively. For the first time, uranium as a naturally occurring radioactive element was found in 20 selected protein spots. The detection limits for P, S, Cu, Zn and U were determined in singular protein spots with 0.0013, 1.29, 0.029, 0.063, and 0.000 01 mg g(-1), respectively. A combination of LA-ICPMS with matrix-assisted laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry (MALDI-FTICR-MS) was applied for the identification of selected protein spots from human brain protein separated by 2D gel electrophoresis. Combining MALDI-FTICR-MS for the structure analysis of metal- and phosphorus-containing human brain proteins with LA-ICPMS, the direct analysis of heteroelements on separated proteins in 2D gels can be performed. For quantification of analytical LA-ICPMS data, the number of sulfur atoms per protein (and following the sulfur concentration) determined by MALDI-FTICR-MS was used for internal standardization. From the known sulfur concentration in protein, the concentration of other heteroelements was calculated. In addition, the number of phosphorylation and the phosphorylation sites of phosphorylated proteins in the human brain sample detected by LA-ICPMS were determined by MALDI-FTICR-MS. This technique allows the study of posttranslational modifications in human brain proteins.     

Determinations of rare earth element abundance and U-Pb age of zircons using multispot laser ablation-inductively coupled plasma mass spectrometry

We have developed a new calibration technique for multielement determination and U-Pb dating of zircon samples using laser ablation-inductively coupled plasma mass spectrometry (ICPMS) coupled with galvanometric optics. With the galvanometric optics, laser ablation of two or more sample materials could be achieved in very short time intervals (~10 ms). The resulting sample aerosols released from different ablation pits or different solid samples were mixed and homogenized within the sample cell and then transported into the ICP ion source. Multiple spot laser ablation enables spiking of analytes or internal standard elements directly into the solid samples, and therefore the standard addition calibration method can be applied for the determination of trace elements in solid samples. In this study, we have measured the rare earth element (REE) abundances of two zircon samples (Nancy 91500 and Pre?ovice) based on the standard addition technique, using a direct spiking of analytes through a multispot laser ablation of the glass standard material (NIST SRM612). The resulting REE abundance data show good agreement with previously reported values within analytical uncertainties achieved in this study (10% for most elements). Our experiments demonstrated that nonspectroscopic interferences on 14 REEs could be significantly reduced by the standard addition technique employed here. Another advantage of galvanometric devices is the accumulation of sample aerosol released from multiple spots. In this study we have measured the U-Pb age of a zircon sample (LMR) using an accumulation of sample aerosols released from 10 separate ablation pits of low diameters (~8 μm). The resulting (238)U-(206)Pb age data for the LMR zircons was 369 ± 64 Ma, which is in good agreement with previously reported age data (367.6 ± 1.5 Ma). (1) The data obtained here clearly demonstrate that the multiple spot laser ablation-ICPMS technique can become a powerful approach for elemental and isotopic ratio measurements in solid materials.     

Magnetic Sector ICPMS with Desolvating Micronebulization: Interference-Free Subpicogram Determination of Rare Earth Elements in Natural Samples

A new method has been developed combining desolvating micronebulization with magnetic sector inductively coupled plasma mass spectrometry (ICPMS) for the analysis of all 14 stable rare earth elements (REEs) in small samples of marine particulate matter. Application is demonstrated for REEs in suspended particles from a deep ocean hydrothermal vent plume and a geological reference material. A 100-fold reduction in oxide formation, relative to standard nebulizer-spray chamber sample introduction, makes oxide interference correction negligible, even for samples that are very enriched in Ba and light REEs. Enriched isotopes for one light and one heavy REE ((145)Nd and (171)Yb) are used as both isotope dilution and internal standards, providing determination of all the REEs in one analysis. This standardization scheme eliminates the need for multimass drift correction used previously to achieve acceptable accuracy with external standardization techniques. Instead, the method exploits capabilities for accurate and precise determination of isotope ratios, a principal strength of ICPMS, and the mass-independent sensitivity of electric field scans on our double-focusing instrument. We demonstrate overall precision of ≤2% (1σ) and accuracy better than 6% for all the REEs (except Er = 8.7%), based on comparison to recommended values for USGS certified reference material BHVO-1 (basalt). This performance is similar to that obtained by full isotope dilution mass spectrometric techniques, but the new method is far simpler, requires 5 min sample(-)(1), and avoids interferences introduced by complex mixtures of enriched isotopes. Sensitivity of (1.2-1.4) × 10(6) counts s(-)(1) ppb(-)(1) and background intensities of 2-60 counts s(-)(1) provide excellent detection limits of 1-40 ppq, a 100-fold improvement on established ICPMS methods. The low sample introduction rate (100 μL min(-)(1)) allows unprecedented absolute detection limits of 1-20 fg.     

Off-line coupling of capillary electrophoresis to substrate-assisted laser desorption inductively coupled plasma mass spectrometry

A novel off-line coupling of capillary electrophoresis (CE) and inductively coupled plasma mass spectrometry (ICPMS) is reported here. The coupling interface is based on the connection of a separation capillary to a deposition capillary via a liquid junction maintaining high separation efficiency and sample utilization due to the self-focusing effect and lack of pressure-induced flow in comparison with nebulizer-like interfaces. The separation is recorded in the form of droplets of CE effluent on a suitable substrate--a poly(ethylene terephthalate) glycol (PETG) sample plate placed inside a partially evacuated chamber. Substrate-assisted laser desorption (SALD) is used to vaporize the sample fractions and to enable further transfer to the ICPMS. The mechanism of SALD is examined using model samples deposited on a variety of substrates. The highest response is obtained for a PETG substrate; sample desorption due to ablation of PETG is found to outweigh direct ablation of sample. Detection limits are given for several metal elements. Finally, a rapid (2.5-min), high-resolution separation of Cr(III)/Cr(VI) species injected in subpicomolar quantity is shown.     

Application of nanosecond-UV laser ablation-inductively coupled plasma mass spectrometry for the isotopic analysis of single submicrometer-size uranium particles

For the first time, laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) was used to carry out isotopic measurement on single submicrometer-size uranium particles. The analytical procedure was applied on two particle-containing samples already analyzed in the same laboratory by established techniques for particle analysis: combination of the fission track technique with thermo-ionization mass spectrometry (FT-TIMS) and secondary ion mass spectrometry (SIMS). Particles were extracted from their initial matrix with ethanol and deposited on a polycarbonate disk where they were fixed in a layer of an organic compound (collodion). Prior to the isotopic analysis, particles were precisely located on the disk's surface by scanning electron microscopy (SEM) for one sample and using the fission track technique for the other sample. Most of the particles were smaller than 1 μm, and their (235)U content was in the femtogram range. (235)U/(238)U ratios were successfully analyzed for all located particles using a nanosecond-UV laser (Cetac LSX 213 nm) coupled to a quadrupole-based ICPMS (Thermo "X-Series II"). LA-ICPMS results, although less precise and accurate (typically 10%) than the ones obtained by FT-TIMS and SIMS due to short (20-40 s), transient, and noisy signals, are in good agreement with the certified values or with the results obtained with other techniques. Thanks to good measurement efficiency (~6 × 10(-4)) and high signal/noise ratio during the analysis, LA-ICPMS can be considered a very promising technique for fast particle analysis, provided that uranium-bearing particles are fixed on the sample holder and located prior to isotope measurement.     

Trace analyses of arsenic in drinking water by inductively coupled plasma mass spectrometry: high resolution versus hydride generation

A magnetic sector inductively coupled plasma mass spectrometer (ICPMS) was applied to the determination of arsenic in drinking water samples using standard liquid sample introduction in the high-resolution mode (M/delta M = 7800) and hydride generation in the low-resolution mode (M/delta M = 300). Although high mass resolution ICPMS allowed the spectral separation of the argon chloride interference, the accompanying reduction in sensitivity at high resolution compromised detection and determination limits to 0.3 and 0.7 microgram/L, respectively. Therefore, a hydride generation sample introduction method, utilizing a new membrane gas-liquid separator design, was developed to overcome the chloride interference. Due to the high transport efficiency and the 50-100 times higher sensitivity at M/delta M = 300, the HG-ICPMS method resulted in an over 2000-fold increase in relative sensitivity. The routine detection and quantification limits were 0.3 and 0.5 ng/L, respectively. The results for both methods applied to the analysis of over 400 drinking water samples showed very good agreement at concentrations above 1 microgram/L. For concentrations between 0.01 and 1 microgram/L, only HG-ICPMS provided accurate quantitative results. Membrane desolvation, mixed-gas plasmas, and the addition of organic solvents for the reduction of the ArCl+ interference were also investigated and evaluated for trace As determination.     

Portable laser ablation sampling device for elemental fingerprinting of objects outside the laboratory with laser ablation inductively coupled plasma mass spectrometry

Laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) is a powerful method for elemental fingerprinting of solid samples in a quasi-nondestructive manner. In order to extend the field of application to objects outside the laboratory, a portable laser ablation sampling device was assembled using a diode pumped solid state laser and fiber-optics. The ablated materials were sampled on membrane filters and subsequently quantified by means of LA-ICPMS. The analytical performance of this approach was investigated for glass and gold reference materials. Accuracies of better than 20% were reached for most elements and typical limits of detection were found to be in the range of 0.01-1 μg/g. In summary, this approach combines spatially resolved sampling with the detection power of ICPMS and enables elemental fingerprinting of objects which cannot be transferred to the laboratory, e.g., archeological artifacts in museums.     

Analysis of protein phosphorylation by capillary liquid chromatography coupled to element mass spectrometry with 31P detection and to electrospray mass spectrometry

A method for phosphopeptide identification by capillary liquid chromatography (muLC) interfaced alternatively to element mass spectrometry (inductively coupled plasma mass spectrometry, ICPMS) and to electrospray ionization mass spectrometry (ESI-MS) is described. ICPMS is used for 31P detection and ESI-MS provides the corresponding molecular weight information. Alignment of the two separate muLC runs is performed using the baseline distortion at the elution front, which shows up in both muLC-ICPMS and muLC-ESI-MS. Both a quadrupole and a magnetic sector field mass analyzer were used in combination with ICP. The detection limit achieved for the muLC-ICP-HRMS runs is approximately 0.1 pmol of phosphopeptide injected. Without any further precautions, contamination by phosphate-containing compounds at this level was found to be uncritical. The method is demonstrated for the analysis of a complex mixture of synthetic phosphopeptides and a set of tryptic digests of three phosphoproteins. These include beta-casein, activated human MAP kinase ERK1, and protein kinase A catalytic subunit. The tryptic phosphopeptides of these proteins could all be detected and identified by our new strategy. Analysis of three fractions of protein kinase A catalytic subunit with different phosphorylation status gives direct access to the order in which the phosphorylation of the four phosphorylation sites occurs. The two most important aspects of using muLC-ICPMS with 31P detection for phosphopeptide identification are (i) that a high selectivity is achieved and (ii) that the signal intensity is independent of the chemical form of phosphorus and directly proportional to the molar amount of 31P in the muLC eluate. Thus, muLC-ICPMS with 31P detection is introduced as a new, robust, and specific method in phosphoproteomics.     

Depth analysis of polymer-coated steel samples using near-infrared femtosecond laser ablation inductively coupled plasma mass spectrometry

The viability of near-infrared femtosecond laser ablation (fs-LA) inductively coupled plasma mass spectrometry (ICPMS) for the in-depth analysis of polymer coatings over galvanized steel substrates has been studied. A good depth resolution was obtained modifying the femtosecond Gaussian beam to a flat-top beam by using a liquid-crystal display. In order to avoid mixing of information coming from successive shots, a low repetition rate was accomplished and signals were monitored shot by shot. Different kinds of coatings were used to demonstrate the capability of femtosecond ablation for depth-profiling analysis. Ablation was conducted under He atmosphere, after sample cell Ar was admixed. The depth profiles obtained by LA-ICPMS are in good agreement with those obtained by GD-OES for the three analyzed samples. In cases where due to averaging over several millimeter sample roughness determines the depth resolution of GD-OES, it was found that LA-ICPMS achieves better depth resolution due to the better lateral resolution. The depth resolution obtained by LA-ICPMS was found to be 240 nm and 2.3 microm, for a hot-dip galvanized steel (HDGS) and a polymer-polymer-coated HDGS, respectively, compared to the 2.2 and 4.5 microm achieved with GD-OES for the same samples.     

电感耦合等离子体质谱在长寿命放射性核素分析中的应用

电感耦合等离子体质谱(Inductively Coupled Plasma Mass Spectrometer,ICP-MS)具有灵敏度高、检出限低、线性动态范围宽和可以进行多元素同时测定及同位素比测量等优点,是一种具有广阔前景的痕量(超痕量)无机多元素分析技术.ICP-MS检测半衰期大于几百年的放射性核素优于放射计数...     

Microbeam Characterization of Corning Archeological Reference Glasses: New Additions to the Smithsonian Microbeam Standard Collection

An initial study of the minor element, trace element, and impurities in Corning archeological references glasses have been performed using three microbeam techniques: electron probe microanalysis (EPMA), laser ablation ICP-mass spectrometry (LA ICP-MS), and secondary ion mass spectrometry (SIMS). The EPMA results suggest a significant level of heterogeneity for a number of metals. Conversely, higher precision and a larger sampling volume analysis by LA ICP-MS indicates a high degree of chemical uniformity within all glasses, typically <2 % relative (1 σ). SIMS data reveal that small but measurable quantities of volatile impurities are present in the glasses, including H at roughly the 0.0001 mass fraction level. These glasses show promise for use as secondary standards for minor and trace element analyses of insulating materials such as synthetic ceramics, minerals, and silicate glasses.     

Inductively coupled plasma mass spectrometry with on-line leaching: a method to assess the mobility and fractionation of elements

A new technique has been developed to assess the mobility and site of specific elements in complex natural materials such as rocks. Concentration profiles during leaching were obtained by pumping reagents (water, 1% HNO3, 10% HNO3, 30% HNO3), either continuously or with flow injection, through a microcolumn of sample while continuously monitoring analyte signals by inductively coupled plasma mass spectrometry (ICPMS). Compared to batch extraction procedures normally used, the approach involves minimal sample preparation and reduced contamination since the leaching is performed in a closed system. Continuous on-line monitoring also allows a greater resolution of the various phases reacting with given reagent. Compared to continuous leaching, flow injection increased the resolution of the various phases using discrete injections of reagents while reducing reagent consumption and minimizing etching of the MS interface. Furthermore, sensitivity was preserved by injecting into air instead of an aqueous carrier. Whether in the continuous or flow injection modes, the proposed approach provides real-time data on what phases are breaking down and what metals are released. It can therefore be used to design effective leaching strategies and to trace isotopic compositions. However, the resulting spectra are complex and the correct determination of some elements requires high-resolution ICPMS.     

Detection of multiple proteins on one spot by laser ablation inductively coupled plasma mass spectrometry and application to immuno- microarray with element-tagged antibodies

Inductively coupled plasma mass spectrometry (ICPMS) has been successfully used for the detection of element-tagged biomolecules with the advantage of multielement capability. However, this technique cannot be used for microarray detection due to the necessity to dissolve the elemental tags before introducing them to the plasma source. Here, we report the detection of multiple proteins on each spot of the immuno-microarray by laser ablation ICPMS. alpha-Fetoprotein IgG (AFP), carcinoembryonic antigen (CEA), and human IgG, as model proteins, have been detected on the basis of sandwich-type immunoreactions on a microarray with Sm3+-labeled AFP antibody, Eu3+-labeled CEA antibody, and Au-labeled goat-anti-human IgG (GAH) as labeled antibodies. The detection limits were 0.20, 0.14, and 0.012 ng mL-1 (3sigma) with the RSD of 5.7%, 2.6%, and 2.3% at the concentration of 1.0 ng mL-1 for AFP, CEA, and human IgG, respectively. The present detection method permits detecting multiple analytes from each spot of microarray with a spatial resolution at micrometer range, which can alleviate the stress to fabricate high-density arrays. Furthermore, the substrate materials and immobilized proteins do not interfere with the detection. The present technique provides a new strategy for readout of microarray.     

Isotope dilution mass spectrometry — A primary method of measurement and its role for RM certification

This article describes the application of isotope dilution mass spectrometry (IDMS) to the field of reference material (RM) characterisation focusing on the approach, which is applied by the IDMS group at BAM. Emphasis is placed on IDMS measurements of highest analytical quality. Basic principles as well as the equation system are being recalled. Different calibration strategies, such as single, double or triple IDMS, are critically reviewed and the achievable uncertainties are discussed. Differences in the application of thermal ionization mass spectrometry (TIMS) and inductively coupled plasma mass spectrometry (ICPMS) are discussed as well as differences between different types of mass spectrometers such as single collector versus multi-collector or quadrupole versus magnetic sector instruments. Possible sources of errors and bias are mentioned and correction models introduced and applied within the past years are discussed. Several examples for RM characterisations in the field of elemental analysis are shown, each demonstrating excellent analytical quality. In general it can be stated that IDMS is the most important reference method for elemental analysis, offering highest accuracy and precision or smallest measurement uncertainties, when properly applied. Thus IDMS represents by far the best suited reference method for RM characterisation. Due to its universal applicability IDMS offers sufficient potential to follow future needs in analytical chemistry as well as in the RM sector     

Evaluation of inductively coupled plasma mass spectrometry as an elemental detector for supercritical fluid chromatography

Supercritical fluid chromatography coupled with inductively coupled plasma mass spectrometry shows high potential for the determination at ultratrace levels of organometallic compounds of environmental interest. In this study the determination of organotin compounds at ultratrace levels is demonstrated. In this work a supercritical fluid chromatography/inductively coupled plasma mass spectrometry (SFC/ICPMS) interface was developed. Separation of tetraalkyltin compounds shows detection levels in the subpicogram range (0.034 pg for tetrabutyltin; 0.047 pg for tetraphenyltin). The linear ranges are over 3 orders magnitude (1-1000 pg). The reproducibility of sample injections are better than 5% RSD.     

Detection, identification, and quantification of selenoproteins in a candidate human plasma standard reference material

To understand the effect of Se supplementation on health, it is critical to accurately assess the Se status in the human body by measuring reliable biomarkers. The preferred biomarkers of the Se status are selenoprotein P (SelP) and glutathione peroxidase 3 (GPx3) along with selenoalbumin (SeAlb), but there is still a real need for reference methods and reference materials to validate their measurements. Therefore, this work presents a systematic approach to provide quality control data in selenoprotein measurements. This approach combines online isotope dilution affinity liquid chromatography (LC) coupled to inductively coupled plasma mass spectrometry (ICPMS), laser ablation ICPMS, and tandem mass spectrometry (MS/MS) to identify and quantify SelP, GPx3, and SeAlb in a human plasma reference material SRM 1950. Quantitative determinations of SelP, GPx3, and SeAlb were 50.2 ± 4.3, 23.6 ± 1.3, and 28.2 ± 2.6 ng g(-1) as Se, respectively. The subsequent identification of the selenoproteins included nine SelP peptides, including two selenopeptides and nine GPx3 peptides, while albumin was identified with a protein coverage factor >95%. The structural elucidation of selenoproteins in the target Se affinity fractions in SRM 1950 provides information needed for method validation and quality control measurements of selenoproteins and therefore the selenium status in human plasma.