Jochen Vogl

Precision and accuracy in isotope ratio measurements by plasma source mass spectrometry

Precise and accurate isotope ratio measurements are an important task in many applications such as isotope dilution mass spectrometry, bioavailability studies or the determination of isotope variations in geological and cosmic samples. There is much more interest in ICP-MS for isotope ratio determinations at present compared with GDMS, which is preferred for the direct measurement of the isotopic composition of metallic solid samples. Spectroscopic interferences and a limited abundance sensitivity can influence the accuracy of isotope ratio determinations by GDMS and ICP-MS. In addition, in ICP-MS the space charge effect always influences the accuracy and a nozzle separation effect may also contribute to the total mass bias. Using a quadrupole ICP-MS the mass discrimination per mass unit can be >10% for elements with mass numbers <10, about 1–5% for mass numbers in the range of 20–120 and only <1% for heavier elements. Mass discrimination is strongly dependent on the potential of the different lenses of the ion optics and on the nebulizer gas flow. Even in magnetic sector field ICP-MS instruments a distinct mass discrimination is observed. Different procedures such as calibration by substances of consistent natural isotopic composition of the same or a neighbouring element and by isotopic standard reference materials, respectively, in combination with various mathematical functions, linear and exponential ones, are used for mass bias correction. In addition to the ion counting statistics, stability of the ion current is one of the most important topics which influences the precision of isotope ratio determinations. Magnetic sector field instruments, producing flat topped peak shapes, coupled with a multi-collector system for simultaneous measurement of different isotopes achieve the best relative standard deviation in the range of typically 0.005–0.02%, which is only comparable with precisions obtained by TIMS. However, ICP-TOFMS also has the potential for similar results. Typical relative standard deviations for other types of plasma source mass spectrometers for isotope ratio determinations are as follows: GDMS 0.1–1, quadrupole ICP-MS 0.1–0.5, and high resolution ICP-MS 0.05–0.2%.

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 example iodate or selenite, whereas the species-unspecific mode must be applied in all cases where the structure and composition of the species is unknown, for example, for metal complexes with humic substances. For accurate determinations by the isotope dilution technique the mass discrimination effect must also be taken into account. Iodate, iodide and organoiodine species, including those of humic substances, have been analysed in mineral, drinking and environmental water samples by coupling different liquid chromatographic methods with ICP-IDMS. Heavy metal complexes with humic substances in water samples of different origin have been characterized by size exclusion/ICP-IDMS. The possibilities of determining different environmental selenium species are discussed and the results for the analysis of selenite and selenate, which has been carried out by GC/ICP-IDMS after converting these species into a volatile piazselenol compound, are presented.

Development and validation of a method to determine the boron isotopic composition of crop plants.

We present a comprehensive chemical and mass spectrometric method to determine boron isotopic compositions of plant tissue. The method including dry ashing, a three-step ion chromatographic boron-matrix separation, and (11)B/(10)B isotope ratio determinations using the Cs(2)BO(2)(+) graphite technique has been validated using certified reference and quality control materials. The developed method is capable to determine δ(11)B values in plant tissue down to boron concentrations of 1 mg/kg with an expanded uncertainty of ≤1.7‰ (k = 2). The determined δ(11)B values reveal an enormous isotopic range of boron in plant tissues covering three-quarters of the natural terrestrial occurring variation in the boron isotopic composition. As the local environment and anthropogenic activity mainly control the boron intake of plants, the boron isotopic composition of plants can be used for food provenance studies.

Boron Isotope Fractionation in Bell Pepper

Various plant compartments of a single bell pepper plant were studied to verify the variability of boron isotope composition in plants and to identify possible intra-plant isotope fractionation. Boron mass fractions varied from 9.8 mg/kg in the fruits to 70.0 mg/kg in the leaves. Boron (B) isotope ratios reported as δ11B ranged from -11.0‰ to +16.0‰ (U ≤ 1.9‰, k=2) and showed a distinct trend to heavier δ11B values the higher the plant compartments were located in the plant. A fractionation of Δ11Bleaf-roots = 27‰ existed in the studied bell pepper plant, which represents about about 1/3 of the overall natural boron isotope variation (ca. 80‰). Two simultaneous operating processes are a possible explanation for the observed systematic intra-plant δ11B variation: 1) B is fixed in cell walls in its tetrahedral form (borate), which preferentially incorporates the light B isotope and the remaining xylem sap gets enriched in the heavy B isotope and 2) certain transporter preferentially transport the trigonal 11B-enriched boric acid molecule and thereby the heavy 11B towards young plant compartments which were situated distal of the roots and typically high in the plant. Consequently, an enrichment of the heavy 11B isotope in the upper young plant parts located at the top of the plant could explain the observed isotope systematic. The identification and understanding of the processes generating systematic intra-plant δ11B variations will potentially enable the use of B isotope for plant metabolism studies.

A new two-stage separation procedure for the IDMS based quantification of low Pd and Pt amounts in automotive exhaust emissions

A two-step separation procedure for the quantification of Pd and Pt in automotive exhaust emissions using isotope dilution mass spectrometry was established using a combination of cation and anion exchange chemistry. AG 50W-X12 was used as cation exchange resin and DGA as weakly basic anion exchange resin. This procedure enabled the effective separation of Pd and Pt from the matrix and from interfering elements. Additionally Pd and Pt were collected in separate chromatographic fractions, which increased the precision of the isotope ratio determination by separate measurements using single collector sector field ICPMS. The analytical procedure was validated by analysing the synthetically prepared samples and the certified reference materials BCR-723 (road dust) and IAEA-450 (algae). For the SI-traceable results complete uncertainty budgets were calculated yielding relatively expanded uncertainties (k = 2) of ≈1% for analyte masses in the ng range. Procedure blanks of 55 pg Pd and 3 pg Pt were obtained. The detection limits were calculated as 12 pg for Pd and 7 pg for Pt. Additionally, Pd and Pt blank levels of different filter materials are presented as well as the first results for automotive exhaust particles collected on cellulose filters.

Report of the CCQM-K123: trace elements in biodiesel fuel

The CCQM-K123 key comparison was organized by the Inorganic Analysis Working Group (IAWG) of CCQM to assess and document the capabilities of the national metrology institutes (NMIs) or the designated institutes (DIs) to measure the mass fractions of sodium, calcium, potassium, magnesium phosphorous and sulfur in biodiesel fuel (BDF). The National Metrology Institute of Japan (NMIJ) and National Institute of Standards and Technology (NIST) acted as the coordinating laboratories. Results were submitted by 11 NMIs and DIs. The participants used different measurement methods, though most of them used inductively coupled plasma-mass spectrometry (ICP-MS), isotope dilution technique with ICP-MS and inductively coupled plasma-optical emission spectrometry (ICP-OES) with microwave acid digestion. The material was quite challenging and a number of questions were raised at the IAWG meeting. Concerning S, the variation in S results between participants, particularly those using IDMS methods was discussed at the IAWG meeting. BAM, NIST and NMIJ reviewed their experimental conditions, results and/or uncertainty calculations for IDMS. According to the additional evaluation and investigation, the variances between the revised results became smaller than the original one, the revised results were overlapping between IDMS measurements of S content at the k=2 level. It is not possible to calculate a KCRV with values being modified after submission. It was concluded that this KC does not support S measurements. Accounting for relative expanded uncertainty, comparability of measurement results for each of Na, Ca, K, Mg and P was successfully demonstrated by the participating NMIs or DIs. It is expected that sodium, calcium, potassium, magnesium and phosphorus at mass fractions greater than approximately 0.1 mg/kg, 0.1 mg/kg, 0.05 mg/kg, 0.05 mg/kg and 0.1 mg/kg respectively in biodiesel fuel and similar matrices (fuels and oils etc.) can be determined by each participant using the same technique(s) employed for this key comparison to achieve similar uncertainties mentioned in the present report. Furthermore, the results of this key comparison can be utilized along with the IAWG core capability approach.

Reference measurement procedures for the quantification of platinum-group elements (PGEs) from automotive exhaust emissions

The major source of the anthropogenic platinum group element (PGE) emission is attributed to the use of catalytic converters in automobiles. This paper describes the work performed by three National Metrology Institutes (Laboratoire national de métrologie et d’essais, by the Physikalisch-technische bundesanstalt, Bundesanatalt für materialforschung und prûfung), in the framework of the Joint Research Project ‘PartEmission’ under the European Metrology Research Program. An analytical procedure based on a cationic exchange protocol and the isotope dilution or standard addition using an Inductived Coupled Plasma Mass Spectrometer, ICP-MS, for the quantification of the elements Pt, Pd and Rh from automotive exhaust emissions is described. Results obtained on a road dust certified reference (BCR 723) material showed a good agreement with the certified values, at ng/g levels, and relative expanded uncertainties within the range of 7–10%. Analysis of filters impacted with automotive exhaust particle emissions (from a diesel engine) showed the amount of collected PGE at levels of 10–1000 pg/filter. Their quantifications followed the developed analytical protocol that had been carried out with relative expanded uncertainties in the range of a few per cent up to 20% per filter. Nevertheless, a lack of homogeneity between the filters was observed, making the comparison between the project partners difficult in the sake of the validation of their analytical procedures on real samples.

CHAPTER 8:Measurement Strategies

Designing an appropriate measurement strategy for a particular analytical question is not always a simple task, since a number of factors have to be considered, whereby some of them might be difficult to define. A set of key questions generally precede the experimental design in analytical measurements and help to choose the measurement strategy, which is fit for the intended use – in the particular case of the content of this book on sector field mass spectrometry – either for quantification, elemental ratio or isotope ratio analyses, accordingly. A set of considerations such as the definition of the analyte and the measurand, matrix composition, background levels, working range, requested measurement uncertainty or the availability of certified reference materials, contribute to the design of a measurement. Within the following sections, the focus will be mainly on considerations with respect to calibration in elemental and isotopic analysis. The basic principles of various calibration strategies (e.g. external calibration, internal normalization, standard addition, isotope dilution) for quantification will be described along with calibration strategies used in isotope ratio mass spectrometry (e.g. internal/external intra- and inter- elemental corrections, double spike techniques, isotope pattern deconvolution). Finally, the most relevant equation models for the correction of instrumental isotopic fractionation are given.