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Introduction
The isotope-ratio mass spectrometer (IRMS) allows the precise measurement of mixtures of
naturally occurring isotopes.[4] Most instruments used for precise determination of isotope ratios are
of the magnetic sector type. This type of analyzer is superior to the quadrupole type in this field of
research for two reasons. First, it can be set up for multiple-collector analysis, and second, it gives
high-quality 'peak shapes'. Both of these considerations are important for isotope-ratio analysis at
very high precision and accuracy.[3]
Isotope-ratio mass spectrometer used to measure stable isotope ratios, with gas bench in foreground
It is critical that the sample be processed before entering the mass spectrometer so that only a
single chemical species enters at a given time. Generally, samples are combusted or pyrolyzed and
the desired gas species (usually hydrogen (H 2), nitrogen (N2), carbon dioxide (CO2), or sulfur dioxide
(SO2)) is purified by means of traps, filters, catalysts and/or chromatography.
The two most common types of IRMS instruments are continuous flow [7] and dual inlet. In dual inlet
IRMS, purified gas obtained from a sample is alternated rapidly with a standard gas (of known
isotopic composition) by means of a system of valves, so that a number of comparison
measurements are made of both gases. In continuous flow IRMS, sample preparation occurs
immediately before introduction to the IRMS, and the purified gas produced from the sample is
measured just once. The standard gas may be measured before and after the sample or after a
series of sample measurements. While continuous-flow IRMS instruments can achieve higher
sample throughput and are more convenient to use than dual inlet instruments, the yielded data is of
approximately 10-fold lower precision.
Schematic diagram of a SHRIMP instrument illustrating the ion beam path. After Figure 4, Williams, 1998. [9]
An alternative approach used to measure the relative abundance of radiogenic isotopes when
working with a solid surface is secondary-ion mass spectrometry (SIMS). This type of ion-microprobe
analysis normally works by focusing a primary (oxygen) ion beam on a sample in order to generate a
series of secondary positive ions that can be focused and measured based on their mass/charge
ratios.
SIMS is a common method used in U-Pb analysis, as the primary ion beam is used to bombard the
surface of a single zircon grain in order to yield a secondary beam of Pb ions. The Pb ions are
analyzed using a double focusing mass spectrometer that comprises both an electrostatic and
magnetic analyzer. This assembly allows the secondary ions to be focused based on their kinetic
energy and mass-charge ratio in order to be accurately collected using a series of Faraday cups. [10]
A major issue that arises in SIMS analysis is the generation of isobaric interference between
sputtered molecular ions and the ions of interest. This issue occurs with U-Pb dating as Pb ions have
essentially the same mass as HfO 2+.[11] In order to overcome this problem, a sensitive high-resolution
ion microprobe (SHRIMP) can be used. A SHRIMP is a double-focusing mass spectrometer that
allows for a large spatial separation between different ion masses based on its relatively large size.
For U-Pb analysis, the SHRIMP allows for the separation of Pb from other interfering molecular ions,
such as HfO2+.
For isotopes occurring at extremely low levels, accelerator mass spectrometry (AMS) can be used.
For example, the decay rate of the radioisotope 14C is widely used to date organic materials, but this
approach is limited to relatively large samples no more than a few thousand years old. AMS
extended the range of 14C dating to about 60,000 years BP, and is about 10 6 times more sensitive
than conventional IRMS.
AMS works by accelerating negative ions through a large (mega-volt) potential, followed by charge
exchange and acceleration back to ground. During charge exchange, interfering species can be
effectively removed. In addition, the high energy of the beam allows the use of energy-loss
detectors, that can distinguish between species with the same mass/charge ratio. Together, these
processes allow the analysis of extreme isotope ratios above 10 12.