Manfred Gröning

Comprehensive inter-laboratory calibration of reference materials for delta O-18 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)a 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 per thousand, an artificially enriched reference water (delta(18)O of +78.91 per thousand) and two barium sulfates (one depleted and one enriched in (18)O) were prepared and calibrated relative to VSMOW2b and SLAP reference waters. These materials were used to calibrate the other isotopic reference materials in this study, which yielded: Reference material delta(18)O and estimated combined uncertainty IAEA-602 benzoic acid+71.28 +/- 0.36 per thousand USGS 35 sodium nitrate+56.81 +/- 0.31 per thousand IAEA-NO-3 potassium nitrate+25.32 +/- 0.29 per thousand IAEA-601 benzoic acid+23.14 +/- 0.19 per thousand IAEA-SO-5 barium sulfate+12.13 +/- 0.33 per thousand NBS 127 barium sulfate+8.59 +/- 0.26 per thousand VSMOW2 water 0 per thousand IAEA-600 caffeine-3.48 +/- 0.53 per thousand IAEA-SO-6 barium sulfate-11.35 +/- 0.31 per thousand USGS 34 potassium nitrate-27.78 +/- 0.37 per thousand SLAP water-55.5 per thousand 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 delta(18)O should be analyzed with internationally distributed isotopic nitrates, and likewise for sulfates and organics. Authors reporting relative differences of oxygen-isotope ratios (delta(18)O) of nitrates, sulfates, or organic material should explicitly state in their reports the delta(18)O values of two or more internationally distributed nitrates (USGS 34, IAEA-NO-3, and USGS 35), 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 delta(18)O values at a later time should it become necessary.The high-temperature reduction technique for analyzing delta(18)O and delta(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.

Atomic weights of the elements 2013 (IUPAC Technical Report)

Abstract 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(238U)/N(235U)=137.8(1).

International Stable Isotope Reference Materials

Publisher Summary This chapter discusses the most important international stable isotope reference materials that define six scales for the elements hydrogen, carbon, nitrogen, oxygen and sulfur. The availability and the proper use of suitable reference materials is one of the basic preconditions to ensure the comparability of stable isotope ratio measurements as performed by different laboratories. Comments are given on isotope reference materials for the elements lithium, boron and chlorine. Certain basic requirements for the used reference materials have to be fulfilled The problem of a proper terminology for reference materials and terms proposed for general use with the intention to achieve better consistency is discussed in the chapter. The available reference materials are intended to calibrate local laboratory standards that are prepared by the individual laboratories. The reference materials are not intended to be used themselves for quality control purposes. The rules that should be applied for an optimal calibration using available reference materials, regardless of the element under consideration are listed. The recent situation, demands and future trends for new isotope reference materials are also discussed.

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 (thermal conversion/elemental analyzer) reduction unit using a semi-automated sealing apparatus can yield reproducibilities (1 standard deviation) of delta(2)H and delta(18)O measurements of 1.0 per thousand and 0.06 per thousand, respectively. These silver tubes containing reference waters may be preferred for the 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 the mass of water sealed in tubes (in a range of 200-400 microg) can be as good as 1%. Approximately 99% of the sealed silver tubes are satisfactory (leak free). Although silver tubes sealed with reference waters are robust and can be shaken or heated to 110 degrees 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 the water will be lost. The tubes 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 users of this method are cautioned to apply the necessary corrections for evaporation, back exchange with laboratory atmospheric moisture, and blanks.

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, C16 n-alkanes, n-C20-fatty acid methyl esters (FAMEs), glycines, and l-valines, together with polyethylene powder and string, one n-C17-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.

Improved water δ2H and δ18O calibration and calculation of measurement uncertainty using a simple software tool

The calibration of all δ(2)H and δ(18)O measurements on the VSMOW/SLAP scale should be performed consistently, based on similar principles, independent of the instrumentation used. The basic principles of a comprehensive calibration strategy are discussed taking water as example. The most common raw data corrections for memory and drift effects are described. Those corrections result in a considerable improvement in data consistency, especially in laboratories analyzing samples of quite variable isotopic composition (e.g. doubly labelled water). The need for a reliable uncertainty assessment for all measurements is discussed and an easy implementation method proposed. A versatile evaluation method based on Excel macros and spreadsheets is presented. It corrects measured raw data for memory and drift effects, performs the calibration and calculates the combined standard uncertainty for each measurement. It allows the easy implementation of the discussed principles in any user laboratory. Following these principles will improve the comparability of data among laboratories.

Calibration of δ17O and δ18O of international measurement standards – VSMOW, VSMOW2, SLAP, and SLAP2

Due to exhaustion of the two primary calibration materials, Vienna Standard Mean Ocean Water (VSMOW) and Standard Light Antarctic Precipitation (SLAP), two replacement materials, VSMOW2 and SLAP2, were created with isotopic compositions as close as possible to the original standards in their D/H and (18)O/(16)O ratios. Measurements of the delta(17)O composition constitute therefore an appropriate independent check of the achieved isotopic adjustment. Aliquots from ampoules of VSMOW, VSMOW2, SLAP, and SLAP2 were fluorinated by BrF(5) and analyzed using a dual-inlet Delta E mass spectrometer. VSMOW2 and SLAP2 were found to be indistinguishable from VSMOW and SLAP, respectively, in their delta(17)O and delta(18)O values within measurement uncertainties. This result is a confirmation of the successful isotopic matching of VSMOW2 and SLAP2 to their predecessors. Further checks of the delta(17)O value of SLAP2 seem desirable.

Ratios for light‐element isotopes standardized for better interlaboratory comparison

Stable isotope-ratio measurements of the light elements have been used in increasingly important ways to understand processes in geochemistry, hydrology, oceanography, atmospheric sciences, environmental studies, and many other fields. Progress in these fields requires better precision and reproducibility of stable isotope-ratio measurements. Some laboratories are claiming accuracies of 0.02‰; or better for δ13C and δ180. However, δ13C and δ180 analyses of the same sample by different laboratories can differ by more than 0.3‰. Recognizing that isotopic analyses of the same homogeneous material reported from different credible laboratories should yield the same isotopic composition within the uncertainty of the measurements, the International Atomic Energy Agency (IAEA) held an Advisory Group Meeting on stable isotope reference and intercomparison materials for light elements in Vienna from December 11 to 14, 1995.

Residence times and age distributions of spring waters at the Semmering catchment area, Eastern Austria, as inferred from tritium, CFCs and stable isotopes

The groundwater system in the mountainous area of Semmering, Austria, was studied by environmental tracers in several karst springs. The tracers used included stable isotopes (18O, 2H), tritium (3H) and chlorofluorocarbons (CFCs). The tracers provided valuable information in regard to (1) the mean altitude of the spring catchment areas; (2) the residence time and age distribution of the spring waters; and (3) the interconnection of the springs to a sinkhole. The combination of the stable isotopic data and the topography/geology provided the estimates of the mean altitudes of the catchment areas. Based on the stable isotopic data the recharge temperature of the spring waters was estimated. The smoothing of precipitations isotopic signal in spring discharge provided information on the minimum transit time of the spring waters. Due to short observation time, 3H data alone cannot be used for describing the mean residence time of the karst waters. CFCs, though useful in recognizing the co-existence of young (post-1993) water with old (CFC-free) water, could not be used to resolve age distribution models. It is shown in this article, however, that the combined use of tritium and CFCs can provide a better assessment of models to account for different groundwater age distributions. In Appendix A, a simplified method for collecting groundwater samples for the analysis of CFCs is described. The method provides a real facilitation for fieldwork. Test data are given for this sampling method in regard to potential contamination by atmospheric CFCs.

Increasing the performance of tritium analysis by electrolytic enrichment

Several improvements are described for the existing tritium enrichment system at the Isotope Hydrology Laboratory of the International Atomic Energy Agency for processing natural water samples. The improvements include a simple method for pretreatment of electrolytic cells to ensure a high tritium separation factor, an improved design of the exhaust system for explosive gases, and a vacuum distillation line for faster initial preparation of water samples for electrolytic enrichment and for tritium analysis. Achievements included the reduction of variation of individual enrichment parameters of all cells to less than 1% and an improvement of 50% of the stability of the background mean. It resulted in an improved detection limit of less than 0.4 TU (at 2s), important for application of tritium measurements in the future at low concentration levels, and resulted in measurement precisions of±0.2 TU and±0.15 TU for liquid scintillation counting and for gas proportional counting, respectively. †Updated paper: originally presented on the IAEA International Symposium “Quality Assurance for Analytical Methods in Isotope Hydrology” (August 2004, Vienna).