IRMS—See Isotope ratio mass spectrometry

Fig. 6.12 Sample pretreatment and conversion of organic compounds into gases for isotope ratio mass spectrometry (IRMS). The reductive pyrolysis is normally performed on glassy carbon (for a summary see e.g. [ 1291). In case of coupled HPLC-IRMS for determination wet oxidation is used [ 122f In the routine isotope ratio analysis of water often isotope equilibration with gases are used for 0-analysis CO2 [ 130], for S H-analysis H2 gas in the presence of Pt [131]. Recently an on-line method for S O and in water has been described showing dual-inlet like performance [ 132]. Low-temperature pyrolysis in connection with GC is used for compound fragmentation with the aim of partial isotope pattern analysis [133]. TC-EA = thermo conversion elemental analyser...

Fig. 6.14 Schematic diagram of a multi-dimensional gas chromatographic-pyrolysis-isotope ratio mass spectrometry (MDGC-P-IRMS) device. After [210] with kind permission of the American Chemical Society. For application see Fig. 6.20...

This book is not intended to cover important branches of mass spectrometry that provide accurate and precise quantitative measurements of relative concentrations, e.g., of variations in isotopic ratios of an element by isotope ratio mass spectrometry (IRMS) and accelerator mass spectrometry (AMS). Rather, this book is mainly concerned with determinations of absolute amount of substance (see Chapter 1 for a definition and explanation), particularly for compounds present at trace levels in complex matrices. (The only exception is the inclusion of a brief description of methods used to determine differences in levels of proteins in living cells or organisms subjected to different stimuli, e.g., disease state vs normal state). 

In the early days of mass spectrometry, research was focused on gas source isotope ratio mass spectrometry (IRMS) or thermal ionization mass spectrometry (TIMS), with as the main aim the determination of the isotopic composition and molar masses of the elements. Since the 1940s, isotope ratio measurements have also been used for the determination of isotope ratios involving a radiogenic nuclide and for quantitative element determination via isotope dilution (see also Chapter 8). The age of the solar system and the Earth were also of particular interest within isotope ratio science. With the establishment and improvement of TIMS instrumentation, the awareness of the importance of precision and accuracy and the need to be able to reproduce a result in another laboratory grew, while... 

The use of carbon isotopes to study DOC is becoming more prevalent due to technological advances in mass spectrometry. DOC generally occurs in natural waters in low concentrations, typically ranging between 0.5 ppm and 10 ppm carbon (Thurman, 1985 see Chapter 5.10). Thus, several liters to tens of liters of water were once necessary to extract enough DOC for conventional dual gas-inlet isotopic analysis. Today, automated total organic carbon analyzers (TOCs) are commercially available, and have been successfully interfaced with continuous flow isotope ratio mass spectrometers (CF-IRMS) for stable isotopic measurements of samples containing ppb concentrations of DOC (e.g., St-Jean, 2003). 

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