Here, we show the
potential and applicability of the novel GC-combustion-MS
approach as a nitrogen-selective GC detector. Operating requirements
to achieve reproducible and compound-independent formation of volatile
NO species as a selective N-signal during the combustion step are
described. Specifically, high temperatures (≥1000 °C)
and post-column O2 flows (0.4 mL min–1 of 0.3% O2 in He) turned out to be necessary when using
a vertical oven without makeup flow (prototype #1). In contrast, the
use of a horizontal oven with 1.7 mL min–1 He as
an additional makeup flow (prototype #2) required milder conditions
(850 °C and 0.2 mL min–1). A detection limit
of 0.02 pg of N injected was achieved, which is by far the lowest
ever reported for any GC detector. Equimolarity, linearity, and peak
shape were also adequate. Validation of the approach was performed
by the analysis of a certified reference material obtaining accurate
(2% error) and precise (2% RSD) results. Robustness was tested with
the analysis of two complex samples with different matrices (diesel
and biomass pyrolysis oil) and N concentration levels. Total N determined
after the integration of the whole chromatograms (524 ± 22 and
11,140 ± 330 μg N g–1, respectively)
was in good agreement with the reference values (497 ± 10 and
11,000 ± 1200 μg N g–1, respectively).
In contrast, GC-NCD results were lower for the diesel sample (394
± 42 μg N g–1). Quantitative values for
the individual and families of N species identified in the real samples
by parallel GC–MS and additional GC × GC–MS analyses
were also obtained using a single generic internal standard.