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Abstract No.: TuP-150
Session: New Instrumentation
Presentation date: Tue, Aug 29, 2006
Presentation time: 14:30 – 16:00

GC-MS Sensitivity Approaching OFN Limits with Difficult Compounds

Aviv Amirav1, Alexander B. Fialkov1

1 Tel Aviv University, Tel Aviv, Israel

Correspondence address: Aviv Amirav, Tel Aviv University, School of Chemistry, Ramat Aviv, Tel Aviv, 69978 Israel.

Web site: http://www.tau.ac.il/chemistry/amirav

Keywords: Ionization, Electron; Mass Spectrometry, Gas Chromatography; Molecular Beam; MS/MS, Gas Chromatography.

Novel aspect: Highest GC-MS sensitivity and how to achieve it, particularly for samples that are difficult for analysis.

 

GC-MS sensitivity is typically characterized and defined with octafluoronaphthalene (OFN), and low femtogram limits of detection (LOD) are specified for it by all the major vendors. However, GC-MS LOD's for the majority of real samples in common matrices are a few orders of magnitude higher than with OFN, and users seldom encounter 1 pg LOD in SIM mode with their analytes. This sensitivity difference is defined by us as "the OFN gap". In fact, sensitivity is not a simple parameter, but rather it is characterized and defined by a set of experimental conditions including the analyzed sample, sample matrix, analysis method and even the GC-MS system history.
A novel GC-MS with Supersonic Molecular Beam (SMB) was used for this study, named 1200-SMB. The GC column output was mixed with helium make up gas, total of 90 ml/min, and transferred through a heated transfer line to a supersonic nozzle. The sample compounds expanded from the supersonic nozzle into a vacuum chamber, were vibrationally cooled, skimmed and collimated into a SMB. The vibrationally cold sample compounds passed a fly-through dual cage electron ionization ion source where they were ionized by 70 eV electrons with 10-15 mA emission current. The ions were focused by ion lens system, deflected 90? degrees by an ion mirror and entered the original Varian 1200 MS for their mass analysis.
We explored the GC-MS parameters which affects and defines its sensitivity, and the following features are reported that contributes to the 1200-SMB sensitivity: a) The molecular ion is enhanced; b) Ion source peak tailing and degradation are eliminated; c) Sample elution temperatures from the GC are lowered; d) The range of thermally labile and low volatility compounds that are amenable for analysis is significantly increased; e) Column bleed and ghost peaks are reduced through sample elution at lower temperatures; f) Vacuum background noise is eliminated; g) Mass independent noise is eliminated; h) Compatibility with large volume injections is improved; i) Matrix interferences are reduced through enhanced molecular ion and MS-MS. As a result, the 1200-SMB detection limits with standard compounds are much closer to its OFN LOD, even in complex matrices.
We demonstrated the achievement of <1 fg OFN LOD milestone (SIM, m/z=272). More importantly, we demonstrated LOD of 2 fg for a more realistic compound such as diazinon and 10 fg for underivatized testosterone that is considered as not amenable for GC-MS analysis. In comparison with standard GC-MS we measured sensitivity enhancement factors of 24 for dimethoate, 30 for methylstearate, 50 for cholesterol, 50 for permethrin, >400 for methomyl and >2000 for C32H66. In general, the harder the compound analysis the greater is the 1200-SMB sensitivity gain. Thus, the 1200-SMB increases the relative sensitivity particularly for those compounds that are the bottleneck of the whole analysis.