Jacqueline L. Mann

Revised δ34S Reference Values for IAEA Sulfur Isotope Reference Materials S-2 and S-3

Revised delta(34)S reference values with associated expanded uncertainties (95% confidence interval (C.I.)) are presented for the sulfur isotope reference materials IAEA-S-2 (22.62 +/- 0.16 per thousand) and IAEA-S-3 (-32.49 +/- 0.16 per thousand). These revised values are determined using two relative-difference measurement techniques, gas source isotope ratio mass spectrometry (GIRMS) and double-spike multi-collector thermal ionization mass spectrometry (MC-TIMS). Gas analyses have traditionally been considered the most robust for relative isotopic difference measurements of sulfur. The double-spike MC-TIMS technique provides an independent method for value-assignment validation and produces revised values that are both unbiased and more precise than previous value assignments. Unbiased delta(34)S values are required to anchor the positive and negative end members of the sulfur delta (delta) scale because they are the basis for reporting both delta(34)S values and the derived mass-independent Delta(33)S and Delta(36)S values.

Final report on key comparison CCQM-K35: Determination of sulfur in diesel fuel

The CCQM-K35 key comparison was organized by the Inorganic Analysis Working Group (IAWG) of the CCQM to test the capabilities of national metrological institutes (NMIs) to measure the sulfur content of diesel fuel at the 40 µg/g level. Four NMIs participated in the key comparison: the Federal Institute for Materials Research and Testing (BAM), the Institute for Reference Materials and Measurements (IRMM), the Laboratory of the Government Chemist (LGC) and the National Institute of Standards and Technology (NIST). NIST designed and coordinated the study. All four laboratories used isotope dilution mass spectrometric techniques, but two laboratories (BAM and NIST) used thermal ionization mass spectrometry (TIMS) and two laboratories (IRMM and LGC) used inductively coupled plasma mass spectrometry (ICP-MS). Both techniques require spiking and combustion of the sample prior to the instrumental determination to quantify the amount of sulfur in the fuels. The agreement among the laboratories was good as evidenced by the small values for both the equivalence statements (Di < 1 µg/g) and the associated uncertainties (ui < 2.3 µg/g). A pilot study (P26.1) was performed concurrently on a kerosene sample at the 8 µg/g level and on the same diesel sample used in this K35 study by laboratories preferring to participate in the pilot study. The results of the pilot study are reported separately. Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (MRA).

Determination of low-level (sub-microgram) sulfur concentrations by isotope dilution multi-collector inductively couple plasma mass spectrometry using a 33S spike and internal normalization for mass bias correction.

RATIONALE The certification of sulfur (S) in Standard Reference Materials™ by the National Institute of Standards and Technology (NIST) has been exclusively performed using isotope dilution thermal ionization mass spectrometry (ID-TIMS). The ID-TIMS measurement method is limited in its capability for low concentration measurements (<1 µg/g) due to the blank associated with the chemical reduction procedure (≈0.2 S µg). Newly developed materials and applications, such as biofuels made from soy and nanomedicine, pose a challenge to the ID-TIMS technique because of their very low concentrations (<<1 µg/g) of S. As described here, a measurement technique with low S blanks is essential for low-level S measurements. METHODS An isotope dilution (ID) multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) method combined with an internal normalization approach for mass bias correction has been used to determine low-level S concentrations in synthetically prepared mixtures using a (33)S-enriched spike material. Dilute sulfur solutions (1 µg S/g) were prepared from NIST SRM 3154 (Sulfate Spectrometric Solution) to test the capability of this technique for measuring very low-level S concentrations. RESULTS The concentration results for each solution were 0.983 ± 0.004 µg/g (95% CI, n = 2, k = 2), 1.006 ± 0.005 µg/g (95% CI, n = 2, k = 2), and 0.999 ± 0.003 µg/g (95% CI, n = 2, k = 2), in excellent agreement with the gravimetric determination, deviating less than 0.35% and suggesting the technique can yield unbiased and accurate results. The blanks averaged 13 ± 0.0017 ng S (1s). CONCLUSIONS The data results provide a clear indication that the ID-MC-ICP-MS method for the determination of low-level S concentrations is feasible. The more than one order of magnitude reduction of the blanks suggests that it is a better alternative to the ID-TIMS method for very low S materials such as are encountered in biofuels and some biochemical species. Published 2012. This article is a US Government work and is in the public domain in the USA.

Measurement of the δ34S value in methionine by double spike multi‐collector thermal ionization mass spectrometry using Carius tube digestion

Methionine is an essential amino acid and is the primary source of sulfur for humans. Using the double spike ((33)S-(36)S) multi-collector thermal ionization mass spectrometry (MC-TIMS) technique, three sample bottles of a methionine material obtained from the Institute for Reference Materials and Measurements have been measured for delta(34)S and sulfur concentration. The mean delta(34)S value, relative to Vienna Canyon Diablo Troilite (VCDT), determined was 10.34 +/- 0.11 per thousand (n = 9) with the uncertainty reported as expanded uncertainties (U). These delta(34)S measurements include a correction for blank which has been previously ignored in studies of sulfur isotopic composition. The sulfur concentrations for the three bottles range from 56 to 88 microg/g. The isotope composition and concentration results demonstrate the high accuracy and precision of the DS-MC-TIMS technique for measuring sulfur in methionine.

Neutron activation of NIST surrogate post-detonation urban debris (SPUD) candidate SRMs

Despite their importance, there is a dearth of post-detonation nuclear forensics standard reference materials (SRMs) suitable for analysis traceable back to a national standard. Accordingly, the nuclear forensics community has requested SRMs be produced that mimic post-detonation fallout debris that include actinides, urban materials, fission products, and activation products. The National Institute of Standards and Technology (NIST), in partnership with the National Physical Laboratory and with support from the Federal Bureau of Investigation, have developed two surrogate post-detonation urban debris (SPUD) candidate SRMs to mimic the “rubble” of a city after an improvised nuclear device detonation. NIST SPUD samples were irradiated at The University of Texas TRIGA reactor, then analyzed via gamma-ray spectroscopy for short-lived, medium-lived, and long-lived fission and activation products.

New determination of the 229Th half-life

A new determination of the 229Th half-life was made based on measurements of the 229Th massic activity of a high-purity solution for which the 229Th molality had previously been measured. The 229Th massic activity was measured by direct comparison with SRM 4328C using 4παβ liquid scintillation counting, NaI counting, and standard addition liquid scintillation counting. The massic activity was confirmed by isotope dilution alpha spectrometry measurements. The calculated 229Th half-life is (7825 ± 87) years (k = 2), which is shorter than the three most recent half-life determinations but is consistent with these values within uncertainties.