TABLE IV

Partial List of Potential Problems That Can Occur in the Direct Injection GC/MS Analysis on Aqueous Extracts (SVOC Analysis) That Could Lead to Omission of Compounds, with a Suggestion on How to Potentially Avoid These Omissions

Direct Injection GC/MS of Organic Extracts
Type of ProblemDescription of ProblemPotential OmissionsHow to Avoid Omissions
Liquid/Liquid Extraction of Aqueous Extracts prior to analysisCompounds with a low partitioning into the organic phase might not be extracted via a Liquid/Liquid ExtractionCaprolactam, Pentaerythritol, etc. …Verify the response of those compounds in other analytical screening methods (e.g., LC/MS APCI/ESI direct injection; derivatization GC/MS)
ChromatographyCompounds at levels high enough to cause detector saturation which may mask co-eluting compoundsDiethylhexyl phthalate from PVC, etc. …Review chromatograms to surface potential compounds that could be masked and verify the response of those compounds in other analytical screening methods (e.g., LC/MS APCI/ESI direct injection; derivatization GC/MS)
ChromatographyCompounds eluting in the higher quantities causing a broad hump (e.g., Hydrocarbons for Rubbers) that could mask co-eluting compoundsIrgafos 168, BADGE related Compounds, etc. …Screening the GC/MS chromatogram with an internal database could discover and identify these compounds (after deconvolutiona). Verify the response of those compounds in other analytical screening methods (e.g., LC/MS APCI/ESI direct injection; derivatization GC/MS)
Sample introductionThermolabile compounds may be partially or fully degraded in the inlet systemSilanes, n-nitrosamines, DINCH, Irgacure 907, n-alkylamines converted to N-methylene-n-alkylamines, pentaerythritol monostearate converted to pentaerythritol, etc. …Having run authentic standards of each individual compound when building the IDB will show which compounds potentially will degrade, to what extent, and what could be formed as artifact.
Consider another orthogonal analytical method which addresses the compounds (e.g., LC/MS (ESI or APCI) or other) without degradation
Sample Preparation or Introductioncompounds react with extraction solvent (during extraction or in GC-inlet) leading to false extractablesEster formation for acids when extracting with Ethanol or IPAConsider use another organic solvent that does not react with the extractable (Hexane, dichloromethane). Capture such circumstances in an internal database.
Sample introductionHigh boiling compounds remain in the inlet system and are not be transferred to the chromatographic columnHigh boiling Fatty Acids (>C24), Higher MW Polymer Additives.The method's capabilities with respect to such compounds will be established during method optimization.
Verify the response of those compounds in other analytical screening methods (e.g., LC/MS APCI/ESI; derivatization GC/MS)
ChromatographySome compounds with specific functional groups will show sub-optimal chromatography or will not elute.Perfluorinated compounds, High MW Acids, Amines, thiols, sulfonic acids, epoxidized oils, etc. …Experience with the analytical method will reveal compounds (with specific functional groups) that may show no/low responses or bad chromatography.
Verify the response of those compounds in other analytical screening methods (e.g., LC/MS APCI/ESI; derivatization GC/MS)
Mass SpectrometryCompounds with higher MW may be missed because they fall outside the of the scanned mass rangeIrganox 1076, Irgafos 168 Ox, tetrabromobisphenol A, etc. …Experience with the analytical method will reveal compounds that may fall outside the MS detector range.
Make the MS-scan range broader.
Verify the response of those compounds in other analytical screening methods allow a proper safety assessment (e.g., LC/MS APCI/ESI; derivatization GC/MS)
  • a An example of the power of mass spectral deconvolution – in combination with the use of an internally developed database – is given in Figure 7 of this document.