Da. Merritt et al., PERFORMANCE AND OPTIMIZATION OF A COMBUSTION INTERFACE FOR ISOTOPE RATIO MONITORING GAS-CHROMATOGRAPHY MASS-SPECTROMETRY, Analytical chemistry, 67(14), 1995, pp. 2461-2473
Conditions and systems for on-line combustion of effluents from capill
ary gas chromatographic columns and for removal of water vapor from pr
oduct streams were tested. Organic carbon in gas chromatographic peaks
15 s wide and containing up to 30 nmol of carbon was quantitatively c
onverted to CO2 by tubular combustion reactors, 200 x 0.5 mm, packed w
ith CuO or NiO. No auxiliary source of O-2 was required because oxygen
was supplied by metal oxides. Spontaneous degradation of CuO limited
the life of CuO reactors at T > 850 degrees C. Since NiO does not spon
taneously degrade, its use might be favored, but Ni-bound carbon phase
s form and lead to inaccurate isotopic results at T < 1050 degrees C i
f gas-phase O-2 is not added. For all compounds tested except CH4, equ
ivalent isotopic results are provided by CuO at 850 degrees C, NiO + O
-2 (gas-phase mole fraction, 10(-3)) at 1050 degrees C, and NiO at 115
0 degrees C. The combustion interface did not contribute additional an
alytical uncertainty, thus observed standard deviations of C-13/C-12 r
atios were within a factor of 2 of shot-noise limits. For combustion a
nd isotopic analyses of CH4, in which quantitative combustion required
T approximate to 950 degrees C, NiO-based systems are preferred, and
precision is similar to 2 times lower than that observed for other ana
lytes. Water must be removed from the gas stream transmitted to the ma
ss spectrometer or else protonation of CO2 will lead to inaccuracy in
isotopic analyses. Although thresholds for this effect vary between ma
ss spectrometers, differential permeation of H2O through Nafion tubing
was effective in both cases tested, but the required length of the Na
fion membrane was 4 times greater for the more sensitive mass spectrom
eter.