Extending the range of compounds amenable for gas chromatography-mass spectrometric analysis

Alexander B. Fialkov, Alexander Gordin, Aviv Amirav

Research output: Contribution to journalArticlepeer-review


Gas chromatography-mass spectrometry (GC-MS) suffers from a major limitation in that an expanding number of thermally labile or low volatility compounds of interest are not amenable for analysis. We found that the elution temperatures of compounds from GC can be significantly lowered by reducing the column length, increasing the carrier gas flow rate, reducing the capillary column film thickness and lowering the temperature programming rate. Pyrene is eluted at 287°C in standard GC-MS with a 30 m×0.25 mm I.D. column with 1-μm DB5ms film and 1-ml/min He column flow rate. In contrast, pyrene is eluted at 79°C in our "Supersonic GC-MS" system using a 1 m×0.25 mm I.D. column with 0.1-μm DB5ms film and 100-ml/min He column flow rate. A simple model has been invoked to explain the significantly (up to 208°C) lower elution temperatures observed. According to this model, every halving of the temperature programming rate, or number of separation plates (either through increased flow rate or due to reduced column length), results in ∼20°C lower elution temperature. These considerably lower elution temperatures enable the analysis of an extended range of thermally labile and low volatility compounds, that otherwise could not be analyzed by standard GC-MS. We demonstrate the analysis of large polycyclic aromatic hydrocarbons (PAHs) such as decacyclene with ten fused rings, well above the current GC limit of PAHs with six rings. Even a metalloporphirin such as magnesiumoctaethylporphin was easily analyzed with elution temperatures below 300°C. Furthermore, a range of thermally labile compounds were analyzed including carbamates such as methomyl, aldicarb, aldicarbsulfone and oxamyl, explosives such as pentaerythritol tetranitrate, Tetryl and HMX, and drugs such as reserpine (608 a.m.u.). Supersonic GC-MS was used, based on the coupling of a supersonic molecular beam (SMB) inlet and ion sources with a bench-top Agilent 6890 GC plus 5972 MSD. The Supersonic GC-MS provides enhanced molecular ion without any ion source related peak tailing. Thus, the lower GC separation power involved in the analysis of thermally labile and low volatility compounds is compensated by increased separation power of the MS gained from the enhanced molecular ion. Several implications of these findings are discussed, including our conclusion that slower chromatography leads to better analysis of thermally labile compounds.

Original languageEnglish
Pages (from-to)217-240
Number of pages24
JournalJournal of Chromatography A
Issue number2
StatePublished - 4 Apr 2003


  • Elution temperature
  • Gas chromatography-mass spectrometry
  • Supersonic GC-MS
  • Temperature programming
  • Thermally labile compounds


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