Analysis of lignocellulose derived phenolic monomers by headspace solid-phase microextraction and gas chromatography

• HS-SPME/GC–MS – method established for analysis of lignin derived phenolic monomers.
• HS-SPME/GC–MS – parameters optimized for 12 lignin derived phenolic monomers.
• Quantitative analysis in complex aqueous solutions, e.g., lignocellulose hydrolyzates.
• No extensive sample preparation, short sample handling times, and high throughput.
• Method especially suited for fast analysis and for screening.

A headspace solid-phase microextraction method with subsequent GC–MS (HS-SPME/GC–MS) was established for the quantitative analysis of volatile lignin derived phenolic monomers in complex aqueous solutions. Extraction was done using a polyacrylate fiber. The optimization of HS-SPME – parameters was performed using a multi component model solution of six representative phenolic monomers identified in liquid hot water (LHW) supernatants of hydrothermally treated lignocellulosic biomass: p-coumaric acid, guaiacol, vanillin, acetosyringone, 4-hydroxy-3-methoxyphenylacetone, and acetophenone. Plackett–Burman design was applied for pre-evaluation and 23 central composite designs with star points for parameter optimization. LOQ (S/N > 10) and LOD (S/N > 3) were determined for 12 phenols yielding LOQ of <0.005–618 nM and LOD of <0.005–412 nM. Within-day and between-day tests (n = 6) showed different results for the tested phenols. RSD ranged from 2% to 30% and recovery rates from 99% to 160% in LHW matrix. Tests on storage of LHW supernatants for several weeks indicated a considerable influence of temperature on the stability of the solutions which may even have to be taken into account for auto sampler handling. All in all the method allows a fast and solvent free analysis requiring low sample volumes making it a powerful tool for screening or high-throughput analysis of aqueous solutions of lignin derived aromatics.