Wa. Brand et al., NEW METHODS FOR FULLY AUTOMATED ISOTOPE RATIO DETERMINATION FROM HYDROGEN AT THE NATURAL-ABUNDANCE LEVEL, Isotopes in environmental and health studies, 32(2-3), 1996, pp. 263-273
A variety of methods for measurement of H-2/H-1 from H-2 are evaluated
for their ability to be fully automated and for applicability to auto
mated isotopic analysis of water and organic compounds. Equilibration
of water with H-2 gas with the aid of a platinum catalyst has been com
mercialized into a fully automated sample preparation device. A second
and newer technique, involving injecting water, methane, or other vol
atile organic compounds onto hot chromium in a reactor attached to the
dual inlet system of a gas isotope ratio mass spectrometer, can be in
tegrated with a conventional GC-autosampler to allow automated analysi
s of a variety of substrates. Both techniques result in precisions aro
und 1 parts per thousand(delta notation) on the VSMOW scale, and are f
ast and accurate, and with appropriate mass spectrometers require only
negligible scaling for the SLAP/VSMOW difference. Several experimenta
l methods which show considerable promise employ ''isotope ratio monit
oring'' (irm) inlet systems, in which a carrier gas is used for transp
ort of H-2 to the mass spectrometer. Any such method has to address th
e problem of He ions corrupting the measurement of the H-2 ions. One s
uch approach uses a heated palladium membrane for selective introducti
on of H-2 into the mass spectrometer, and a second involves modificati
ons to the ion optics to control the stray helium ions. Both approache
s have significant limitations that must be overcome before irm techni
ques can be used in routine applications, in particular for measuring
hydrogen isotopes From GC effluents (irm-GCMS).