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ABSTRACT: We report the development of a hyphenated instrument with the capacity to quantitatively characterize aqueous suspended gold nanoparticles (AuNPs) based on a combination of gas-phase size separation, particle counting, and elemental analysis. A customized electrospray-differential mobility analyzer (ES-DMA) was used to achieve real-time upstream size discrimination. A condensation particle counter and inductively coupled plasma mass spectrometer (ICP-MS) were employed as downstream detectors, providing information on number density and elemental composition, respectively, of aerosolized AuNPs versus the upstream size selected by ES-DMA. A gas-exchange device was designed and optimized to improve the conversion of air flow (from the electrospray) to argon flow required to sustain the ICP-MS plasma, the key compatibility issue for instrumental hyphenation. Our work provides the proof of concept and a working prototype for utilizing this construct to successfully measure (1) number- and mass-based distributions; (2) elemental compositions of nanoparticles classified by size, where the size classification and elemental analysis are performed within a single experiment; (3) particle concentrations in both solution (before size discrimination) and aerosol (after size discrimination) phases; and (4) the number of atoms per nanoparticle or the nanoparticle density.
Analytical and Bioanalytical Chemistry 01/2013; · 3.78 Impact Factor
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ABSTRACT: Perchlorate, an inorganic anion, has recently been recognized as an environmental contaminant by the US Environmental Protection Agency. Urine is the preferred matrix for assessment of human exposure to perchlorate. Although the measurement technique for perchlorate in urine was developed in 2005, the calibration and quality assurance aspects of the metrology infrastructure for perchlorate are still lacking in that there is no certified reference material (CRM) traceable to the International System of Units. To meet the quality assurance needs in biomonitoring measurements of perchlorate and the related anions that affect thyroid health, the National Institute of Standards and Technology (NIST), in collaboration with the Centers for Disease Control and Prevention (CDC), developed Standard Reference Material (SRM) 3668 Mercury, Perchlorate, and Iodide in Frozen Human Urine. SRM 3668 consists of perchlorate, nitrate, thiocyanate, iodine, and mercury in urine at two levels that represent the 50th and 95th percentiles, respectively, of the concentrations (with some adjustments) in the US population. It is the first CRM being certified for perchlorate. Measurements leading to the certification of perchlorate were made collaboratively at NIST and CDC using three methods based on liquid or ion chromatography tandem mass spectrometry. Potential sources of bias were analyzed, and results were compared for the three methods. Perchlorate in SRM 3668 Level I urine was certified to be 2.70 ± 0.21 μg L(-1), and for SRM 3668 Level II urine, the certified value is 13.47 ± 0.96 μg L(-1).
Analytical and Bioanalytical Chemistry 08/2012; 404(6-7):1877-86. · 3.78 Impact Factor
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ABSTRACT: In this study, a prototypical thiolated organic ligand, 3-mercaptopropionic acid (MPA), was conjugated on gold nanoparticles (AuNPs), and packing density was measured on an ensemble-averaged basis using inductively coupled plasma optical emission spectrometry. The effects of sample preparation, including centrifugation and digestion, as well as AuNP size and concentration, on recovery were investigated. For AuNPs with diameters of 5, 10, 30, 60, and 100 nm, calculated packing density is independent of size, averaging 7.8 nm(-2) and ranging from 6.7 to 9.0 nm(-2), and is comparable to reported values for MPA and similar short-chain ligands on AuNPs. These preliminary data provide fundamental information on the advantages and limitations of ICP-based analyses of conjugated AuNP systems. Moreover, they provide necessary information for the development of more broadly applicable methods for quantifying nanoparticle-ligand conjugates of critical importance to nanomedicine applications.
Analytical and Bioanalytical Chemistry 02/2012; 403(1):145-9. · 3.78 Impact Factor
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ABSTRACT: NIST has performed preliminary research on applying a calibration methodology based on the method of standard additions to the quantification of peptides via reverse-phase liquid chromatography coupled to inductively coupled plasma mass spectrometry (RPLC-ICP-MS). A microwave-assisted lanthanide labeling procedure was developed and applied to derivatize peptides using the macrocyclic bifunctional chemical chelator DOTA (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid), which significantly improved the lanthanide labeling yield and reduced reaction times compared to benchtop labeling procedures. Biomolecular MS technologies of matrix-assisted laser desorption ionization (MALDI)-MS and electrospray ionization (ESI)-MS/MS were used in concert with ICP-MS to confirm the results of microwave labeling, sample cleanup and standard additions experiments for several test peptides. The calibration scheme is outlined in detail and contextualized against complementary high accuracy calibration strategies currently employed for ICP-MS detection of biomolecules. Standard additions experiments using native, non-isotopic peptide calibrants confirm the simplicity of the scheme and the potential of applying a blending (recombined sample and spike) procedure, facilitating calibration via co-elution of lanthanide labeled peptides. Ways to improve and fully leverage the analytical methodology are highlighted.
Talanta 01/2012; 88:749-58. · 3.79 Impact Factor
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ABSTRACT: Nondestructive analyses using a quadrupole inductively coupled plasma-mass spectrometer (ICP-QMS) and polarizing, multi-target, energy dispersive X-ray fluorescence (PEDXRF) with three-dimensional optics were conducted on Judean coins from the first century BCE and CE to determine the efficacy and limits of these methods for numismatic analyses of coins with a patina. Comparisons with destructive analyses and literature databases demonstrate their value even when corrosion is present. An outstanding question about the dating of Herod Agrippa I or II "canopy" coins that has significance to Biblical historians is used as a case study. Multiple lines of evidence attribute this coin to Agrippa I, with a date of 41 to 45 CE, produced using Faynan (Feinan), Jordan, and Cyprus ores.
Applied Spectroscopy 04/2010; 64(4):384-90. · 1.66 Impact Factor
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Ryna B Marinenko,
Shirley Turner,
David S Simons,
Savelas A Rabb,
Rolf L Zeisler, Lee L Yu,
Dale E Newbury,
Rick L Paul,
Nicholas W M Ritchie,
Stefan D Leigh,
Michael R Winchester,
Lee J Richter,
Douglas C Meier,
Keana C K Scott,
Donna Klinedinst,
John A Small
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ABSTRACT: Bulk silicon-germanium (SiGe) alloys and two SiGe thick films (4 and 5 microm) on Si wafers were tested with the electron probe microanalyzer (EPMA) using wavelength dispersive spectrometers (WDS) for heterogeneity and composition for use as reference materials needed by the microelectronics industry. One alloy with a nominal composition of Si0.86Ge0.14 and the two thick films with nominal compositions of Si0.90Ge0.10 and Si0.75Ge0.25 on Si, evaluated for micro- and macroheterogeneity, will make good microanalysis reference materials with an overall expanded heterogeneity uncertainty of 1.1% relative or less for Ge. The bulk Ge composition in the Si0.86Ge0.14 alloy was determined to be 30.228% mass fraction Ge with an expanded uncertainty of the mean of 0.195% mass fraction. The thick films were quantified with WDS-EPMA using both the Si0.86Ge0.14 alloy and element wafers as reference materials. The Ge concentration was determined to be 22.80% mass fraction with an expanded uncertainty of the mean of 0.12% mass fraction for the Si0.90Ge0.10 wafer and 43.66% mass fraction for the Si0.75Ge0.25 wafer with an expanded uncertainty of the mean of 0.25% mass fraction. The two thick SiGe films will be issued as National Institute of Standards and Technology Reference Materials (RM 8905).
Microscopy and Microanalysis 02/2010; 16(1):1-12. · 3.01 Impact Factor
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ABSTRACT: Two independent liquid chromatography inductively coupled plasma-mass spectrometry (LC/ICP-MS) methods for the separation of arsenic species in urine have been developed with quantification by standard additions. Seven arsenic species have been quantified in a new NIST frozen human urine Standard Reference Material (SRM) 2669 Arsenic Species in Frozen Human Urine, Levels 1 and 2. The species measured were: arsenite (As(III)), arsenate (As(V)), monomethylarsonate (MMA), dimethylarsinate (DMA), arsenobetaine (AB), arsenocholine (AC), and trimethylarsine oxide (TMAO). The purity of each arsenic standard used for quantification was measured as well as the arsenic species impurities determined in each standard. Analytical method limits of detection (L(D)) for the various species in both methods ranged from 0.2 to 0.8 microg L(-1) as arsenic. The results demonstrate that LC/ICP-MS is a sensitive, reproducible, and accurate technique for the determination of low-level arsenic species in urine. Measurements of the arsenic species 3 years after initial production of the SRM demonstrate the stability of the arsenic species in the urine reference material.
Analytical and Bioanalytical Chemistry 02/2010; 396(8):3041-50. · 3.78 Impact Factor
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Ryna B. Marinenko,
Shirley Turner,
David S. Simons,
Savelas A. Rabb,
Rolf L. Zeisler, Lee L. Yu,
Dale E. Newbury,
Rick L. Paul,
Nicholas W.M. Ritchie,
Stefan D. Leigh,
Michael R. Winchester,
Lee J. Richter,
Douglas C. Meier,
Keana C.K. Scott,
Donna Klinedinst,
John A. Small
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ABSTRACT: Bulk silicon-germanium (SiGe) alloys and two SiGe thick films (4 and 5 μm) on Si wafers were tested with the electron probe microanalyzer (EPMA) using wavelength dispersive spectrometers (WDS) for heterogeneity and composition for use as reference materials needed by the microelectronics industry. One alloy with a nominal composition of Si0.86Ge0.14 and the two thick films with nominal compositions of Si0.90Ge0.10 and Si0.75Ge0.25 on Si, evaluated for micro- and macroheterogeneity, will make good microanalysis reference materials with an overall expanded heterogeneity uncertainty of 1.1% relative or less for Ge. The bulk Ge composition in the Si0.86Ge0.14 alloy was determined to be 30.228% mass fraction Ge with an expanded uncertainty of the mean of 0.195% mass fraction. The thick films were quantified with WDS-EPMA using both the Si0.86Ge0.14 alloy and element wafers as reference materials. The Ge concentration was determined to be 22.80% mass fraction with an expanded uncertainty of the mean of 0.12% mass fraction for the Si0.90Ge0.10 wafer and 43.66% mass fraction for the Si0.75Ge0.25 wafer with an expanded uncertainty of the mean of 0.25% mass fraction. The two thick SiGe films will be issued as National Institute of Standards and Technology Reference Materials (RM 8905).
Microscopy and Microanalysis 01/2010; 16(01):1 - 12. · 3.01 Impact Factor
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Applied Spectroscopy 12/2009; 63(12):1406-9. · 1.66 Impact Factor
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ABSTRACT: The certification of Standard Reference Material (SRM is a registered trademark of NIST) 3103a As Spectrometric Solution is based on the gravimetric preparation value that is verified by inductively coupled plasma optical emission spectrometry (ICP-OES) measurements. A disagreement between the gravimetric and the spectrometric values for a batch of As calibration solutions led to the discovery that the solutions contained a mixture of trivalent and pentavalent As species and that the pentavalent species was approximately 8% more sensitive than the trivalent species with ICP-OES determination. The kinetics of the reaction between As metal and nitric acid were studied, and the results were applied to develop a procedure that would consistently produce single-species pentavalent As standards, which eliminates As speciation as a source of measurement bias in the SRM certification process.
Analytical Chemistry 04/2006; 78(5):1651-6. · 5.86 Impact Factor
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ABSTRACT: Owing to the increasing demand for compliance with quality system standards, analytical laboratories may need to demonstrate the traceability of their results to the International System of Units (SI) or to the values of a certified reference material. To do that, they need to demonstrate the components of uncertainty in their analytical work. At NIST, the goal is to demonstrate traceability to SI units to ensure that results are accepted on a worldwide basis. For XRF spectrometry with borate fusion, traceability to SI is achieved through calibration with spectrometric solution standards or high-purity compounds. The method is capable of achieving relative expanded uncertainty estimates (95% confidence level) of 1% or lower. In this paper, the capability is demonstrated for low alloy-steel and an AlTiNbW aerospace alloy. XRF results are compared with certified values and with results from atomic emission methods through a simple bias test. NIST uses the borate fusion/XRF method as part of the value assignment process for Standard Reference Materials®. Copyright © 2004 John Wiley & Sons, Ltd.
X-Ray Spectrometry 10/2004; 34(2):153 - 159. · 1.45 Impact Factor
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ABSTRACT: The detection limit is an important figure of merit for evaluating instrumentation and analytical methods. While the detection limit for techniques using linear calibration functions has been studied extensively, this fundamental metric has rarely been discussed for mass spectrometry that bases the calibration on the principle of isotope dilution. We have developed a formulation for the detection limit for isotope dilution mass spectrometry (IDMS) after a thorough analysis of the uncertainty of IDMS measurements. The new formulation describes the IDMS detection limit as a function of the enrichment of the isotopic spike and the linear calibration detection limits measured at the masses for the isotope ratio measurement.
Analytical Chemistry 09/2002; 74(15):3887-91. · 5.86 Impact Factor
