Triple Isotope Fractionation Exponents of Elements Measured by MC-ICP-MS—An Example of Mg

In most chemical reactions, stable isotopes are fractionated in a mass-dependent manner, yielding correlated isotope ratios in elements with three or more stable isotopes. The proportionality between isotope ratios is set by the triple isotope fractionation exponent θ that can be determined precisely for, e.g., sulfur and oxygen by IRMS, but not for metal(loid) elements due to the lower precision of MC-ICP-MS analysis and smaller isotopic variations. Here, using Mg as a test case, we compute a complete metrologically robust uncertainty budget for apparent θ values and, with reference to this, present a new measurement approach that reduces uncertainty on θ values by 30%. T…

Setting the Scene: Element Determination and its Quality Control in Fractions of Refractory Organic Substances and the Corresponding Original Water Samples

Producing SI-traceable reference values for Cd, Cr and Pb amount contents in polyethylene samples from the Polymer Elemental Reference Material (PERM) project using isotope dilution mass spectrometry

The present paper describes the certification of the amount content of Cd, Cr and Pb in two different polyethylene materials within the third phase of the Polyethylene Elemental Reference Material (PERM) project. The analytical procedure to establish the reference values for Cd, Cr and Pb amount contents in these materials is based on isotope dilution mass spectrometry used as a primary method of measurement. Cd and Pb were measured with inductively coupled plasma-mass spectrometry and Cr with positive thermal ionization-mass spectrometry. The decomposition of the polymer matrix was carried out using a high pressure asher. Reference values for amount content, traceable to the SI-system, hav…

Development of an ICP−IDMS Method for Dissolved Organic Carbon Determinations and Its Application to Chromatographic Fractions of Heavy Metal Complexes with Humic Substances

A sensitive and fast method for direct determinations of dissolved organic carbon (DOC) in bulk samples and in chromatographically separated fractions by inductively coupled plasma isotope dilution mass spectrometry (ICP−IDMS) is developed. A 13C-enriched spike solution of benzoic acid is used for the isotope dilution step. Equal ionization efficiencies are obtained for carbon, independent of the type and molecular weight of the dissolved organic substance, which is the most important precondition for DOC determinations by ICP−IDMS. The detection limits achieved are 0.3 mg L-1 for bulk analyses and 7 × 10-4 μg s-1 for transient signals of chromatographic peaks. The results for different wat…

Determination of heavy metal complexes with humic substances by HPLC/ICP-MS coupling using on-line isotope dilution technique

An isotope dilution mass spectrometric (IDMS) method has been developed for the simultaneous determination of the complexes of 11 heavy metals (Ag, Cd, Cu, Mo, Ni, Pb, Tl, U, W, Zn and Zr) with humic substances (HS) by coupling HPLC with ICP-MS and applying the on-line isotope dilution technique. The HPLC separation was carried out with size exclusion chromatography. This HPLC/ICP-IDMS method was applied to samples from a brown water, ground water, sewage and seepage water as well as for a sample containing isolated fulvic acids. The total contents of heavy metals and of their complexes were analyzed in these samples with detection limits in the range of 5–110 ng/L. The analysis of heavy me…

Structural Investigations: Heavy Metal and Halogen Interactions with Fractions of Refractory Organic Substances Separated by Size-exclusion Chromatography

Diagenetic stability of non-traditional stable isotope systems (Ca, Sr, Mg, Zn) in teeth – An in-vitro alteration experiment of biogenic apatite in isotopically enriched tracer solution

Stable isotope ratios and trace element concentrations of fossil bones and teeth are important geochemical proxies for the reconstruction of diet and past environment in archaeology and palaeontology. However, since diagenesis can significantly alter primary diet-related isotope signatures and elemental compositions, it is important to understand and quantify alteration processes. Here, we present the results of in-vitro alteration experiments of dental tissues from a modern African elephant molar reacted in aqueous solutions at 30 °C and 90 °C for 4 to 63 days. Dental cubes with ≈ 3 mm edge length, comprising both enamel and dentin, were placed into 2 mL of acidic aqueous sol…

Accurate determination of element species by on-line coupling of chromatographic systems with ICP-MS using isotope dilution technique

Abstract The instrumental design for coupling different liquid chromatographic systems such as ion, reversed phase, and size exclusion chromatography as well as capillary gas chromatography, with ICP-MS for the determination of element species is described. For accurate analyses obtaining ‘real time’ concentrations of chromatographic peaks, the isotope dilution mass spectrometric (IDMS) technique is applied. Two different spiking modes are possible, one using species-specific and another one using species-unspecific spike solutions of isotope-enriched labelled compounds. The species-specific mode is only possible for element species well defined in their structure and composition, for examp…