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Willi A. Brand

Publications and source records attributed to Willi A. Brand.

18 recordsLinked to original sources
USGS2021

USGS44, a new high-purity calcium carbonate reference material for δ13C measurements

Rationale The stable carbon isotopic ( δ 13 C) reference material (RM) LSVEC Li 2 CO 3 has been found to be unsuitable for δ 13 C standardization work because its δ 13 C value increases with exposure to atmospheric CO 2 . A new CaCO 3 RM, USGS44, has been prepared to alleviate this situation. Methods USGS44 was prepared from 8 kg of Merck high-purity CaCO 3 . Two sets of δ 13 C values of USGS44 were determined. The first set of values was determined by online combustion, continuous-flow (CF) isotope-ratio mass spectrometry (IRMS) of NBS 19 CaCO 3 ( δ 13 C VPDB = +1.95 milliurey (mUr) exactly, where mUr = 0.001 = 1‰), and LSVEC Li 2 CO 3 ( δ 13 C VPDB = −46.6 mUr exactly), and normalized to the two-anchor δ 13 C VPDB-LSVEC isotope-delta scale. The second set of values was obtained by dual-inlet (DI)-IRMS of CO 2 evolved by reaction of H 3 PO 4 with carbonates, corrected for cross contamination, and normalized to the single-anchor δ 13 C VPDB scale. Results USGS44 is stable and isotopically homogeneous to within 0.02 mUr in 100-μg amounts. It has a δ 13 C VPDB-LSVEC value of −42.21 ± 0.05 mUr. Single-anchor δ 13 C VPDB values of −42.08 ± 0.01 and −41.99 ± 0.02 mUr were determined by DI-IRMS with corrections for cross contamination. Conclusions The new high-purity, well-homogenized calcium carbonate isotopic reference material USGS44 is stable and has a δ 13 C VPDB-LSVEC value of −42.21 ± 0.05 mUr for both EA/IRMS and DI-IRMS measurements. As a carbonate relatively depleted in 13 C, it is intended for daily use as a secondary isotopic reference material to normalize stable carbon isotope delta measurements to the δ 13 C VPDB-LSVEC scale. It is useful in quantifying drift with time, determining mass-dependent isotopic fractionation (linearity correction), and adjusting isotope-ratio-scale contraction. Due to its fine grain size (smaller than 63 μm), it is not suitable as a δ 18 O reference material. A δ 13 C VPDB-LSVEC value of −29.99 ± 0.05 mUr was determined for NBS 22 oil.

Rapid Communications in Mass Spectrometry↗
USGS2018

Preliminary assessment of stable nitrogen and oxygen isotopic composition of USGS51 and USGS52 nitrous oxide reference gases and perspectives on calibration needs

Rationale Despite a long history and growing interest in isotopic analyses of N 2 O, there is a lack of isotopically characterized N 2 O isotopic reference materials (standards) to enable normalization and reporting of isotope‐delta values. Here we report the isotopic characterization of two pure N 2 O gas reference materials, USGS51 and USGS52, which are now available for laboratory calibration ( https://isotopes.usgs.gov/lab/referencematerials.html ). Methods A total of 400 sealed borosilicate glass tubes of each N 2 O reference gas were prepared from a single gas filling of a high vacuum line. We demonstrated isotopic homogeneity via dual‐inlet isotope‐ratio mass spectrometry. Isotopic analyses of these reference materials were obtained from eight laboratories to evaluate interlaboratory variation and provide preliminary isotopic characterization of their δ 15 N, δ 18 O, δ 15 N α , δ 15 N β and site preference ( S P ) values. Results The isotopic homogeneity of both USGS51 and USGS52 was demonstrated by one‐sigma standard deviations associated with the determinations of their δ 15 N, δ 18 O, δ 15 N α , δ 15 N β and S P values of 0.12 mUr or better. The one‐sigma standard deviations of S P measurements of USGS51 and USGS52 reported by eight laboratories participating in the interlaboratory comparison were 1.27 and 1.78 mUr, respectively. Conclusions The agreement of isotope‐delta values obtained in the interlaboratory comparison was not sufficient to provide reliable accurate isotope measurement values for USGS51 and USGS52. We propose that provisional values for the isotopic composition of USGS51 and USGS52 determined at the Tokyo Institute of Technology can be adopted for normalizing and reporting sample data until further refinements are achieved through additional calibration efforts.

Rapid Communications in Mass Spectrometry↗
USGS2017

Optimization of on-line hydrogen stable isotope ratio measurements of halogen- and sulfur-bearing organic compounds using elemental analyzer–chromium/high-temperature conversion isotope ratio mass spectrometry (EA-Cr/HTC-IRMS)

Rationale: Accurate hydrogen isotopic analysis of halogen- and sulfur-bearing organics has not been possible with traditional high-temperature conversion (HTC) because the formation of hydrogen-bearing reaction products other than molecular hydrogen (H2) is responsible for non-quantitative H2 yields and possible hydrogen isotopic fractionation. Our previously introduced, new chromium-based EA-Cr/HTC-IRMS (Elemental Analyzer–Chromium/High-Temperature Conversion Isotope Ratio Mass Spectrometry) technique focused primarily on nitrogen-bearing compounds. Several technical and analytical issues concerning halogen- and sulfur-bearing samples, however, remained unresolved and required further refinement of the reactor systems. Methods: The EA-Cr/HTC reactor was substantially modified for the conversion of halogen- and sulfur-bearing samples. The performance of the novel conversion setup for solid and liquid samples was monitored and optimized using a simultaneously operating dual-detection system of IRMS and ion trap MS. The method with several variants in the reactor, including the addition of manganese metal chips, was evaluated in three laboratories using EA-Cr/HTC-IRMS (on-line method) and compared with traditional uranium-reduction-based conversion combined with manual dual-inlet IRMS analysis (off-line method) in one laboratory. Results: The modified EA-Cr/HTC reactor setup showed an overall H2-recovery of more than 96% for all halogen- and sulfur-bearing organic compounds. All results were successfully normalized via two-point calibration with VSMOW-SLAP reference waters. Precise and accurate hydrogen isotopic analysis was achieved for a variety of organics containing F-, Cl-, Br-, I-, and S-bearing heteroelements. The robust nature of the on-line EA-Cr/HTC technique was demonstrated by a series of 196 consecutive measurements with a single reactor filling. Conclusions: The optimized EA-Cr/HTC reactor design can be implemented in existing analytical equipment using commercially available material and is universally applicable for both heteroelement-bearing and heteroelement-free organic-compound classes. The sensitivity and simplicity of the on-line EA-Cr/HTC-IRMS technique provide a much needed tool for routine hydrogen-isotope source tracing of organic contaminants in the environment. Copyright © 2016 John Wiley & Sons, Ltd.

Rapid Communications in Mass Spectrometry↗
USGS2017

New biotite and muscovite isotopic reference materials, USGS57 and USGS58, for δ2H measurements–A replacement for NBS 30

The advent of continuous-flow isotope-ratio mass spectrometry (CF-IRMS) coupled with a high temperature conversion (HTC) system enabled faster, more cost effective, and more precise δ 2 H analysis of hydrogen-bearing solids. Accurate hydrogen isotopic analysis by on-line or off-line techniques requires appropriate isotopic reference materials (RMs). A strategy of two-point calibrations spanning δ 2 H range of the unknowns using two RMs is recommended. Unfortunately, the supply of the previously widely used isotopic RM, NBS 30 biotite, is exhausted. In addition, recent measurements have shown that the determination of δ 2 H values of NBS 30 biotite on the VSMOW-SLAP isotope-delta scale by on-line HTC systems with CF-IRMS may be unreliable because hydrogen in this biotite may not be converted quantitatively to molecular hydrogen. The δ 2 H VSMOW-SLAP values of NBS 30 biotite analyzed by on-line HTC systems can be as much as 21 mUr (or ‰) too positive compared to the accepted value of − 65.7 mUr, determined by only a few conventional off-line measurements. To ensure accurate and traceable on-line hydrogen isotope-ratio determinations in mineral samples, we here propose two isotopically homogeneous, hydrous mineral RMs with well-characterized isotope-ratio values, which are urgently needed. The U.S. Geological Survey (USGS) has prepared two such RMs, USGS57 biotite and USGS58 muscovite. The δ 2 H values were determined by both glassy carbon-based on-line conversion and chromium-based on-line conversion, and results were confirmed by off-line conversion. The quantitative conversion of hydrogen from the two RMs using the on-line HTC method was carefully evaluated in this study. The isotopic compositions of these new RMs with 1-σ uncertainties and mass fractions of hydrogen are: USGS57 (biotite) δ 2 H VSMOW-SLAP = − 91.5 ± 2.4 mUr ( n = 24) Mass fraction hydrogen = 0.416 ± 0.002% ( n = 4) Mass fraction water = 3.74 ± 0.02% ( n = 4) USGS58 (muscovite) δ 2 H VSMOW-SLAP = − 28.4 ± 1.6 mUr ( n = 24) Mass fraction hydrogen = 0.448 ± 0.002% ( n = 4) Mass fraction water = 4.03 ± 0.02% ( n = 4). These δ 2 H VSMOW-SLAP values encompass typical ranges for solid unknowns of crustal and mantle origin and are available to users for recommended two-point calibration.

Chemical Geology↗
USGS2016

New organic reference materials for hydrogen, carbon, and nitrogen stable isotope-ratio measurements: caffeines, n-alkanes, fatty acid methyl esters, glycines, L-valines, polyethylenes, and oils

An international project developed, quality-tested, and determined isotope−δ values of 19 new organic reference materials (RMs) for hydrogen, carbon, and nitrogen stable isotope-ratio measurements, in addition to analyzing pre-existing RMs NBS 22 (oil), IAEA-CH-7 (polyethylene foil), and IAEA-600 (caffeine). These new RMs enable users to normalize measurements of samples to isotope−δ scales. The RMs span a range of δ 2 H VSMOW-SLAP values from −210.8 to +397.0 mUr or ‰, for δ 13 C VPDB-LSVEC from −40.81 to +0.49 mUr and for δ 15 N Air from −5.21 to +61.53 mUr. Many of the new RMs are amenable to gas and liquid chromatography. The RMs include triads of isotopically contrasting caffeines, C 16 n -alkanes, n -C 20 -fatty acid methyl esters (FAMEs), glycines, and l -valines, together with polyethylene powder and string, one n -C 17 -FAME, a vacuum oil (NBS 22a) to replace NBS 22 oil, and a 2 H-enriched vacuum oil. A total of 11 laboratories from 7 countries used multiple analytical approaches and instrumentation for 2-point isotopic normalization against international primary measurement standards. The use of reference waters in silver tubes allowed direct normalization of δ 2 H values of organic materials against isotopic reference waters following the principle of identical treatment. Bayesian statistical analysis yielded the mean values reported here. New RMs are numbered from USGS61 through USGS78, in addition to NBS 22a. Because of exchangeable hydrogen, amino acid RMs currently are recommended only for carbon- and nitrogen-isotope measurements. Some amino acids contain 13 C and carbon-bound organic 2 H-enrichments at different molecular sites to provide RMs for potential site-specific isotopic analysis in future studies.

Analytical Chemistry↗
USGS2016

Atomic weights of the elements 2013 (IUPAC Technical Report)

The biennial review of atomic-weight determinations and other cognate data has resulted in changes for the standard atomic weights of 19 elements. The standard atomic weights of four elements have been revised based on recent determinations of isotopic abundances in natural terrestrial materials: cadmium to 112.414(4) from 112.411(8), molybdenum to 95.95(1) from 95.96(2), selenium to 78.971(8) from 78.96(3), and thorium to 232.0377(4) from 232.038 06(2). The Commission on Isotopic Abundances and Atomic Weights (ciaaw.org) also revised the standard atomic weights of fifteen elements based on the 2012 Atomic Mass Evaluation: aluminium (aluminum) to 26.981 5385(7) from 26.981 5386(8), arsenic to 74.921 595(6) from 74.921 60(2), beryllium to 9.012 1831(5) from 9.012 182(3), caesium (cesium) to 132.905 451 96(6) from 132.905 4519(2), cobalt to 58.933 194(4) from 58.933 195(5), fluorine to 18.998 403 163(6) from 18.998 4032(5), gold to 196.966 569(5) from 196.966 569(4), holmium to 164.930 33(2) from 164.930 32(2), manganese to 54.938 044(3) from 54.938 045(5), niobium to 92.906 37(2) from 92.906 38(2), phosphorus to 30.973 761 998(5) from 30.973 762(2), praseodymium to 140.907 66(2) from 140.907 65(2), scandium to 44.955 908(5) from 44.955 912(6), thulium to 168.934 22(2) from 168.934 21(2), and yttrium to 88.905 84(2) from 88.905 85(2). The Commission also recommends the standard value for the natural terrestrial uranium isotope ratio, N ( 238 U)/ N ( 235 U)=137.8(1).

Pure and Applied Chemistry↗
USGS2016

Isotopic compositions of the elements 2013 (IUPAC Technical Report)

The Commission on Isotopic Abundances and Atomic Weights (ciaaw.org) of the International Union of Pure and Applied Chemistry (iupac.org) has revised the Table of Isotopic Compositions of the Elements (TICE). The update involved a critical evaluation of the recent published literature. The new TICE 2013 includes evaluated data from the “best measurement” of the isotopic abundances in a single sample, along with a set of representative isotopic abundances and uncertainties that accommodate known variations in normal terrestrial materials.

Pure and Applied Chemistry↗
USGS2016

A new organic reference material, L-glutamic acid, USGS41a, for δ 13 C and δ 15 N measurements − a replacement for USGS41

Rationale The widely used l -glutamic acid isotopic reference material USGS41, enriched in both 13 C and 15 N, is nearly exhausted. A new material, USGS41a, has been prepared as a replacement for USGS41. Methods USGS41a was prepared by dissolving analytical grade l -glutamic acid enriched in 13 C and 15 N together with l -glutamic acid of normal isotopic composition. The δ 13 C and δ 15 N values of USGS41a were directly or indirectly normalized with the international reference materials NBS 19 calcium carbonate ( δ 13 C VPDB = +1.95 mUr, where milliurey = 0.001 = 1 ‰), LSVEC lithium carbonate ( δ 13 C VPDB = −46.6 mUr), and IAEA-N-1 ammonium sulfate ( δ 15 N Air = +0.43 mUr) and USGS32 potassium nitrate ( δ 15 N = +180 mUr exactly) by on-line combustion, continuous-flow isotope-ratio mass spectrometry, and off-line dual-inlet isotope-ratio mass spectrometry. Results USGS41a is isotopically homogeneous; the reproducibility of δ 13 C and δ 15 N is better than 0.07 mUr and 0.09 mUr, respectively, in 200-μg amounts. It has a δ 13 C value of +36.55 mUr relative to VPDB and a δ 15 N value of +47.55 mUr relative to N 2 in air. USGS41 was found to be hydroscopic, probably due to the presence of pyroglutamic acid. Experimental results indicate that the chemical purity of USGS41a is substantially better than that of USGS41. Conclusions The new isotopic reference material USGS41a can be used with USGS40 (having a δ 13 C VPDB value of −26.39 mUr and a δ 15 N Air value of −4.52 mUr) for (i) analyzing local laboratory isotopic reference materials, and (ii) quantifying drift with time, mass-dependent isotopic fractionation, and isotope-ratio-scale contraction for isotopic analysis of biological and organic materials. Published in 2016. This article is a U.S. Government work and is in the public domain in the USA.

Rapid Communications in Mass Spectrometry↗
USGS2015

Isotopic disproportionation during hydrogen isotopic analysis of nitrogen-bearing organic compounds

Rationale High-precision hydrogen isotope ratio analysis of nitrogen-bearing organic materials using high-temperature conversion (HTC) techniques has proven troublesome in the past. Formation of reaction products other than molecular hydrogen (H 2 ) has been suspected as a possible cause of incomplete H 2 yield and hydrogen isotopic fractionation. Methods The classical HTC reactor setup and a modified version including elemental chromium, both operated at temperatures in excess of 1400 °C, have been compared using a selection of nitrogen-bearing organic compounds, including caffeine. A focus of the experiments was to avoid or suppress hydrogen cyanide (HCN) formation and to reach quantitative H 2 yields. The technique also was optimized to provide acceptable sample throughput. Results The classical HTC reaction of a number of selected compounds exhibited H 2 yields from 60 to 90 %. Yields close to 100 % were measured for the experiments with the chromium-enhanced reactor. The δ 2 H values also were substantially different between the two types of experiments. For the majority of the compounds studied, a highly significant relationship was observed between the amount of missing H 2 and the number of nitrogen atoms in the molecules, suggesting the pyrolytic formation of HCN as a byproduct. A similar linear relationship was found between the amount of missing H 2 and the observed hydrogen isotopic result, reflecting isotopic fractionation. Conclusions The classical HTC technique to produce H 2 from organic materials using high temperatures in the presence of glassy carbon is not suitable for nitrogen-bearing compounds. Adding chromium to the reaction zone improves the yield to 100 % in most cases. The initial formation of HCN is accompanied by a strong hydrogen isotope effect, with the observed hydrogen isotope results on H 2 being substantially shifted to more negative δ 2 H values. The reaction can be understood as an initial disproportionation leading to H 2 and HCN with the HCN-hydrogen systematically enriched in 2 H by more than 50 ‰. In the reaction of HCN with chromium, H 2 and chromium-containing solid residues are formed quantitatively.

Rapid Communications in Mass Spectrometry↗
USGS2014

Assessment of international reference materials for isotope-ratio analysis (IUPAC Technical Report)

Since the early 1950s, the number of international measurement standards for anchoring stable isotope delta scales has mushroomed from 3 to more than 30, expanding to more than 25 chemical elements. With the development of new instrumentation, along with new and improved measurement procedures for studying naturally occurring isotopic abundance variations in natural and technical samples, the number of internationally distributed, secondary isotopic reference materials with a specified delta value has blossomed in the last six decades to more than 150 materials. More than half of these isotopic reference materials were produced for isotope-delta measurements of seven elements: H, Li, B, C, N, O, and S. The number of isotopic reference materials for other, heavier elements has grown considerably over the last decade. Nevertheless, even primary international measurement standards for isotope-delta measurements are still needed for some elements, including Mg, Fe, Te, Sb, Mo, and Ge. It is recommended that authors publish the delta values of internationally distributed, secondary isotopic reference materials that were used for anchoring their measurement results to the respective primary stable isotope scale.

Pure and Applied Chemistry↗
USGS2013

Atomic weights of the elements 2011 (IUPAC Technical Report)

The biennial review of atomic-weight determinations and other cognate data has resulted in changes for the standard atomic weights of five elements. The atomic weight of bromine has changed from 79.904(1) to the interval [79.901, 79.907], germanium from 72.63(1) to 72.630(8), indium from 114.818(3) to 114.818(1), magnesium from 24.3050(6) to the interval [24.304, 24.307], and mercury from 200.59(2) to 200.592(3). For bromine and magnesium, assignment of intervals for the new standard atomic weights reflects the common occurrence of variations in the atomic weights of those elements in normal terrestrial materials.

Pure and Applied Chemistry↗
USGS2012

Stable isotope deltas: Tiny, yet robust signatures in nature

Although most of them are relatively small, stable isotope deltas of naturally occurring substances are robust and enable workers in anthropology, atmospheric sciences, biology, chemistry, environmental sciences, food and drug authentication, forensic science, geochemistry, geology, oceanography, and paleoclimatology to study a variety of topics. Two fundamental processes explain the stable isotope deltas measured in most terrestrial systems: isotopic fractionation and isotope mixing. Isotopic fractionation is the result of equilibrium or kinetic physicochemical processes that fractionate isotopes because of small differences in physical or chemical properties of molecular species having different isotopes. It is shown that the mixing of radioactive and stable isotope end members can be modelled to provide information on many natural processes, including 14C abundances in the modern atmosphere and the stable hydrogen and oxygen isotopic compositions of the oceans during glacial and interglacial times. The calculation of mixing fractions using isotope balance equations with isotope deltas can be substantially in error when substances with high concentrations of heavy isotopes (e.g. 13C, 2H, and 18O ) are mixed. In such cases, calculations using mole fractions are preferred as they produce accurate mixing fractions. Isotope deltas are dimensionless quantities. In the International System of Units (SI), these quantities have the unit 1 and the usual list of prefixes is not applicable. To overcome traditional limitations with expressing orders of magnitude differences in isotope deltas, we propose the term urey (symbol Ur), after Harold C. Urey, for the unit 1. In such a manner, an isotope delta value expressed traditionally as−25 per mil can be written as−25 mUr (or−2.5 cUr or−0.25 dUr; the use of any SI prefix is possible). Likewise, very small isotopic differences often expressed in per meg ‘units’ are easily included (e.g. either+0.015 ‰ or+15 per meg can be written as+15 μUr.

Isotopes in Environmental and Health Studies↗
USGS2010

Novel silver tubing method for quantitative introduction of water into high temperature conversion systems for stable hydrogen and oxygen isotopic measurements

A new method to seal water in silver tubes for use in a TC/EA reduction unit using a semi-automated sealing apparatus can yield reproducibilities (1 standard deviation) of δ 2 H and &delta 18 O measurements of 1.0 ‰ and 0.06 ‰, respectively. These silver tubes containing reference waters may be preferred for calibration of H- and O-bearing materials analyzed with a TC/EA reduction unit. The new sealing apparatus employs a computer controlled stepping motor to produce silver tubes identical in length. The reproducibility of mass of water sealed in tubes (in a range of 200 to 400 µg) can be as good as 1 percent. Although silver tubes sealed with reference waters are robust and can be shaken or heated to 110 °C with no loss of integrity, they should not be frozen because the expansion during the phase transition of water to ice will break the cold seals and all water will be lost. They should be shipped in insulated containers. This new method eliminates air inclusions and isotopic fractionation of water associated with the loading of water into capsules using a syringe. The method is also more than an order of magnitude faster than preparing water samples in ordinary Ag capsules. Nevertheless, some laboratories may prefer loading water into silver capsules because expensive equipment is not needed, but they are cautioned to apply the necessary corrections for evaporation, back exchange with laboratory atmospheric moisture, and blank.

Rapid Communications in Mass Spectrometry↗
USGS2010

Correction for the 17O interference in δ(13C) measurements when analyzing CO2 with stable isotope mass spectrometry

Measurements of δ( 13 C) determined on CO 2 with an isotope-ratio mass spectrometer (IRMS) must be corrected for the amount of 17 O in the CO 2 . For data consistency, this must be done using identical methods by different laboratories. This report aims at unifying data treatment for CO 2 IRMS by proposing (i) a unified set of numerical values, and (ii) a unified correction algorithm, based on a simple, linear approximation formula. Because the oxygen of natural CO 2 is derived mostly from the global water pool, it is recommended that a value of 0.528 be employed for the factor λ, which relates differences in 17 O and 18 O abundances. With the currently accepted N( 13 C)/N( 12 C) of 0.011 180(28) in VPDB (Vienna Peedee belemnite) reevaluation of data yields a value of 0.000 393(1) for the oxygen isotope ratio N( 17 O)/N( 16 O) of the evolved CO 2 . The ratio of these quantities, a ratio of isotope ratios, is essential for the 17 O abundance correction: [N( 17 O)/N( 16 O)]/[N( 13 C)/N( 12 C)] = 0.035 16(8). The equation [δ( 13 C) ≈ 45 δ VPDB-CO2 + 2 17 R/ 13 R ( 45 δ VPDB-CO2 – λ 46 δ VPDB-CO2 )] closely approximates δ( 13 C) values with less than 0.010 ‰ deviation for normal oxygen-bearing materials and no more than 0.026 ‰ in extreme cases. Other materials containing oxygen of non-mass-dependent isotope composition require a more specific data treatment. A similar linear approximation is also suggested for δ( 18 O). The linear approximations are easy to implement in a data spreadsheet, and also help in generating a simplified uncertainty budget.

Pure and Applied Chemistry↗
USGS2009

Comprehensive inter-laboratory calibration of reference materials for δ18O versus VSMOW using various on-line high-temperature conversion techniques

Internationally distributed organic and inorganic oxygen isotopic reference materials have been calibrated by six laboratories carrying out more than 5300 measurements using a variety of high-temperature conversion techniques (HTC) in an evaluation sponsored by the International Union of Pure and Applied Chemistry (IUPAC). To aid in the calibration of these reference materials, which span more than 125‰, an artificially enriched reference water ( δ 18 O of +78.91‰) and two barium sulfates (one depleted and one enriched in 18 O) were prepared and calibrated relative to VSMOW2 and SLAP reference waters. These materials were used to calibrate the other isotopic reference materials in this study, which yielded: Reference material δ 18 O and estimated combined uncertainty IAEA-602 benzoic acid +71.28 ± 0.36‰ USGS35 sodium nitrate +56.81 ± 0.31‰ IAEA-NO-3 potassium nitrate +25.32 ± 0.29‰ IAEA-601 benzoic acid +23.14 ± 0.19‰ IAEA-SO-5 barium sulfate +12.13 ± 0.33‰ NBS 127 barium sulfate +8.59 ± 0.26‰ VSMOW2 water 0‰ IAEA-600 caffeine −3.48 ± 0.53‰ IAEA-SO-6 barium sulfate −11.35 ± 0.31‰ USGS34 potassium nitrate −27.78 ± 0.37‰ SLAP water −55.5‰ The seemingly large estimated combined uncertainties arise from differences in instrumentation and methodology and difficulty in accounting for all measurement bias. They are composed of the 3-fold standard errors directly calculated from the measurements and provision for systematic errors discussed in this paper. A primary conclusion of this study is that nitrate samples analyzed for δ 18 O should be analyzed with internationally distributed isotopic nitrates, and likewise for sulfates and organics. Authors reporting relative differences of oxygen-isotope ratios ( δ 18 O) of nitrates, sulfates, or organic material should explicitly state in their reports the δ 18 O values of two or more internationally distributed nitrates (USGS34, IAEA-NO-3, and USGS35), sulfates (IAEA-SO-5, IAEA-SO-6, and NBS 127), or organic material (IAEA-601 benzoic acid, IAEA-602 benzoic acid, and IAEA-600 caffeine), as appropriate to the material being analyzed, had these reference materials been analyzed with unknowns. This procedure ensures that readers will be able to normalize the δ 18 O values at a later time should it become necessary. The high-temperature reduction technique for analyzing δ 18 O and δ 2 H is not as widely applicable as the well-established combustion technique for carbon and nitrogen stable isotope determination. To obtain the most reliable stable isotope data, materials should be treated in an identical fashion; within the same sequence of analyses, samples should be compared with working reference materials that are as similar in nature and in isotopic composition as feasible.

Rapid Communications in Mass Spectrometry↗
USGS2003

Two new organic reference materials for δ13C and δ15N measurements and a new value for the δ13C of NBS 22 oil

Analytical grade L-glutamic acid is chemically stable and has a C/N mole ratio of 5, which is close to that of many of natural biological materials, such as blood and animal tissue. Two L-glutamic acid reference materials with substantially different 13 C and 15 N abundances have been prepared for use as organic reference materials for C and N isotopic measurements. USGS40 is analytical grade L-glutamic acid and has a δ 13 C value of −26.24‰ relative to VPDB and a δ 15 N value of −4.52‰ relative to N 2 in air. USGS41 was prepared by dissolving analytical grade L-glutamic acid with L-glutamic acid enriched in 13 C and 15 N. USGS41 has a δ 13 C value of +37.76‰ and a δ 15 N value of +47.57‰. The δ 13 C and δ 15 N values of both materials were measured against the international reference materials NBS 19 calcium carbonate ( δ 13 C = +1.95‰), L-SVEC lithium carbonate ( δ 13 C = −46.48‰), IAEA-N-1 ammonium sulfate ( δ 15 N = 0.43‰), and USGS32 potassium nitrate ( δ 15 N = 180‰) by on-line combustion continuous-flow and off-line dual-inlet isotope-ratio mass spectrometry. Both USGS40 and USGS41 are isotopically homogeneous; reproducibility of δ 13 C is better than 0.13‰, and that of δ 15 N is better than 0.13‰ in 100-μg amounts. These two isotopic reference materials can be used for (i) calibrating local laboratory reference materials, and (ii) quantifying drift with time, mass-dependent fractionations, and isotope-ratio-scale contraction in the isotopic analysis of various biological materials. Isotopic results presented in this paper yield a δ 13 C value for NBS 22 oil of −29.91‰, in contrast to the commonly accepted value of −29.78‰ for which off-line blank corrections probably have not been quantified satisfactorily.

Rapid Communications in Mass Spectrometry↗
USGS2001

An interlaboratory study to test instrument performance of hydrogen dual-inlet isotope-ratio mass spectrometers

An interlaboratory comparison of forty isotope-ratio mass spectrometers of different ages from several vendors has been performed to test 2 H/ 1 H performance with hydrogen gases of three different isotopic compositions. The isotope-ratio results (unsufficiently corrected for H 3 + contribution to the m/z = 3 collector, uncorrected for valve leakage in the change-over valves, etc.) expressed relative to one of these three gases covered a wide range of values: –630‰ to –790‰ for the second gas and –368‰ to –462‰ for the third gas. After normalizing the isotopic abundances of these test gases (linearly adjusting the δ values so that the gases with the lowest and highest 2 H content were identical for all laboratories), the standard deviation of the 40 measurements of the intermediate gas was a remarkably low 0.85‰. It is concluded that the use of scaling factors is mandatory for providing accurate internationally comparable isotope-abundance values. Linear scaling for the isotope-ratio scales of gaseous hydrogen mass spectrometers is completely adequate.

Fresenius' Journal of Analytical Chemistry↗