Investigating the influence of instrumental parameters and chemical composition on pyrolysis efficiency of peat

To track changes in organic matter (OM) in peat soils, analytical techniques are needed that effectively characterize their chemical components. Pyrolysis-gas chromatography/mass spectrometry is a useful method for obtaining a chemical "fingerprint" of OM. To obtain representative fingerprints, the pyrolysis process should be highly reproducible and representative of the original sample; however, these key indicators for successful volatilization are underreported in the literature. We investigated the influence of instrumental parameters (temperatures, heating rates, sample mass), original organic C and nitrogen (N) content, and instrument type ("slow" vs "flash"), on volatilization of different peat samples by monitoring sample mass loss and changes in organic C and N content before and after pyrolysis. Average percent C by mass volatilized ("C pyrolysis efficiency") across all pyrolysis experiments conducted (mass, instrument types, and settings) was 47.8 +/- 1.8%. Sample mass was not a major driver; however, instrument temperatures, heating rate, and original N content had a significant influence on pyrolysis efficiency. N pyrolysis efficiency occurred at significantly higher rates (56.7-75.8%) than C pyrolysis efficiency (45.1-51.6%). N pyrolysis efficiency was also negatively influenced by decreasing concentrations of original sample N, suggesting that N-containing compounds may undergo preferential volatilization in high pyrolysis temperatures. Our data suggest that C pyrolysis efficiency is relatively insensitive to instrumental parameters; whereas when seeking to identify N-containing compounds, appropriate temperatures and heating rates must be chosen. These results provide an expected range for pyrolysis efficiency as a reference for peat samples analyzed with this technique.