18O/16O ratio measurements of inorganic and organic materials by elemental analysis-pyrolysis-isotope ratio mass spectrometry continuous-flow techniques

We have used a high‐precision, easy, low‐cost and rapid method of oxygen isotope analysis applied to various O‐bearing matrices, organic and inorganic (sulfates, nitrates and phosphates), whose ¹⁸O/¹⁶O ratios had already been measured. It was first successfully applied to ¹⁸O analyses of natural and synthetic phosphate samples. The technique uses high‐temperature elemental analysis–pyrolysis (EA‐pyrolysis) interfaced in continuous‐flow mode to an isotope ratio mass spectrometry (IRMS) system. Using the same pyrolysis method we have been able to generate a single calibration curve for all those samples showing pyrolysis efficiencies independent of the type of matrix pyrolysed. We have also investigated this matrix‐dependent pyrolysis issue using a newly developed pyrolysis technique involving 'purge‐and‐trap' chromatography. As previously stated, silver phosphate being a very stable material, weakly hygroscopic and easily synthesized with predictable ¹⁸O/¹⁶O values, could be considered as a good candidate to become a reference material for the determination of ¹⁸O/¹⁶O ratios by EA‐pyrolysis‐IRMS. Copyright © 2011 John Wiley & Sons, Ltd.     

Isotopic analysis of ethanol: study on 18O/16O measurement using a high‐temperature pyrolysis system coupled to an isotope ratio mass spectrometer

The original article to which this Erratum refers was published in Rapid Commun. Mass Spectrom. 20 ; 2006, 937–940.     

Methods to reduce interference effects in thermal conversion elemental analyzer/continuous flow isotope ratio mass spectrometry delta18O measurements of nitrogen-containing compounds

On-line determination of the oxygen isotopic composition (delta(18)O value) in organic and inorganic samples is commonly performed using a thermal conversion elemental analyzer (TC-EA) linked to a continuous flow isotope ratio mass spectrometry (IRMS) system. Accurate delta(18)O analysis of N-containing compounds (like nitrates) by TC-EA-IRMS may be complicated because of interference of the N(2) peak on the m/z 30 signal of the CO peak. In this study we evaluated the effectiveness of two methods to overcome this interference which do not require any hardware modifications of standard TC-EA-IRMS systems. These methods were (1) reducing the amount of N(2) introduced into the ion source through He dilution of the N(2) peak and (2) an improved background correction on the CO m/z 30 sample peak integration.Our results show that He dilution is as effective as diverting the N(2) peak in order to eliminate this interference. We conclude that the He-dilution technique is a viable method for the delta(18)O analysis of nitrates and other N-containing samples (which are not routinely measured using He dilution) using TC-EA-IRMS, since it can easily be programmed in the standard software of IRMS systems. With the He-dilution technique delta(18)O values of the nitrate isotope standards USGS34, IAEA-N3 and USGS35 were measured using the shortest possible traceability chain to the VSMOW-SLAP scale, and the results were -28.1 +/- 0.1 per thousand, +25.5 +/- 0.1 per thousand and +57.5 +/- 0.2 per thousand, respectively. An improved background correction was also an effective method, but required manual correction of the raw data.     

High-throughput simultaneous determination of plasma water deuterium and 18-oxygen enrichment using a high-temperature conversion elemental analyzer with isotope ratio mass spectrometry

This paper presents a high-throughput method for the simultaneous determination of deuterium and oxygen-18 (18O) enrichment of water samples isolated from blood. This analytical method enables rapid and simple determination of these enrichments of microgram quantities of water. Water is converted into hydrogen and carbon monoxide gases by the use of a high-temperature conversion elemental analyzer (TC-EA), that are then transferred on-line into the isotope ratio mass spectrometer. Accuracy determined with the standard light Antartic precipitation (SLAP) and Greenland ice sheet precipitation (GISP) is reliable for deuterium and 18O enrichments. The range of linearity is from 0 up to 0.09 atom percent excess (APE, i.e. -78 up to 5725 delta per mil (dpm)) for deuterium enrichment and from 0 up to 0.17 APE (-11 up to 890 dpm) for 18O enrichment. Memory effects do exist but can be avoided by analyzing the biological samples in quintuplet. This method allows the determination of 1440 samples per week, i.e. 288 biological samples per week.     

Determination of the 2H/1H, 17O/16O,and 18O/16O isotope ratios in water by means of tunable diode laser spectroscopy at 1.39 microm

We demonstrate the feasibility of the accurate and simultaneous measurement of the 2H/1H, 17O/16O, and 18O/16O isotope ratios in water vapor by means of tunable diode laser spectroscopy. The absorptions are due to the v1 + v3 combination band, observed using a room temperature, distributed feedback (DFB) diode laser at 1.39 microm. The precision of the instrument is approximately 3, 1, and 0.5/1000 for the 2H, 17O, and 18O isotope ratios, respectively, and is at present limited by residual optical feedback to the laser. The signal-to-noise, however, is superior to that obtained in a similar experiment using a color center laser at 2.7 microm. Replacing the current laser with a better unit, we are confident that a precision well below 1/1000 is attainable for all three isotope ratios. The diode laser apparatus is ideally suited for applications demanding a reliable, cheap, and/or portable instrument, such as the biomedical doubly labeled water method and atmospheric sensing.