A variety of potentially inhibitory degradation products are produced during pretreatment of lignocellulosic biomass. Qualitative and quantitative interrogation of pretreatment hydrolysates is paramount to identifying potential correlations between pretreatment chemistries and microbial inhibition in downstream bioconversion processes. In the present study, corn stover, poplar, and pine feedstocks were pretreated under eight different chemical conditions, which are representative of leading pretreatment processes. Pretreatment processes included: 0.7% H(2)SO(4), 0.07% H(2)SO(4), liquid hot water, neutral buffer solution, aqueous ammonia, lime, lime with oxygen pressurization, and wet oxidation. Forty lignocellulosic degradation products resulting from pretreatment were analyzed using high performance liquid chromatography in combination with UV spectroscopy or tandem mass spectrometry detection (HPLC-PDA-MS/MS) and ion chromatography (IC). Of these compounds, several have been reported to be inhibitory, including furfural, hydroxymethyl furfural, ferulic acid, 3,4-dihydroxybenzaldehyde, syringic acid among others. Formation and accumulation of monitored compounds in hydrolysates is demonstrated to be a function of both the feedstock and pretreatment conditions utilized.

Corn stover is one of the leading feedstock candidates for commodity-scale biomass-to-ethanol processing. The composition of water-soluble materials in corn stover has been determined with greater than 90% mass closure in four of five representative samples. The mass percentage of water-soluble materials in tested stover samples varied from 14 to 27% on a dry weight basis. Over 30 previously unknown constituents of aqueous extracts were identified and quantified using a variety of chromatographic techniques. Monomeric sugars (primarily glucose and fructose) were found to be the predominant water-soluble components of corn stover, accounting for 30-46% of the dry weight of extractives (4-12% of the dry weight of feedstocks). Additional constituents contributing to the mass balance for extractives included various alditols (3-7%), aliphatic acids (7-21%), inorganic ions (10-18%), oligomeric sugars (4-12%), and a distribution of oligomers tentatively identified as being derived from phenolic glycosides (10-18%).

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Any valuation of a potential feedstock for bioprocessing is inherently dependent upon detailed knowledge of its chemical composition. Accepted analytical procedures for compositional analysis of biomass water-soluble extracts currently enable near-quantitative mass closure on a dry weight basis. Techniques developed in conjunction with a previous analytical assessment of corn stover have been applied to assess the composition of water-soluble materials in four representative switchgrass samples. To date, analytical characterization of water-soluble material in switchgrass has resulted in >78% mass closures for all four switchgrass samples, three of which have a mass closure of >85%. Over 30 previously unknown constituents in aqueous extracts of switchgrass were identified and quantified using a variety of chromatographic techniques. Carbohydrates (primarily sucrose, glucose, and fructose) were found to be the predominant water-soluble components of switchgrass, accounting for 18-27% of the dry weight of extractives. Total glycans (monomeric and oligomeric sugars) contributed 25-32% to the dry weight of extractives. Additional constituents contributing to the mass balance for extractives included various alditols (2-3%), organic acids (10-13%), inorganic ions (11-13%), and a distribution of oligomers presumed to represent a diverse mixture of lignin-carbohydrate complexes (30-35%). Switchgrass results are compared with previous analyses of corn stover extracts and presented in the context of their potential impact on biomass processing, feedstock storage, and future analyses of feedstock composition.

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A variety of degradation products are produced upon pretreatment of lignocellulosic biomass with dilute acid. To date, the complexity of these samples has significantly limited the scope of efforts to perform summative analyses of degradation products. Qualitative and quantitative interrogation of hydrolysates is also paramount to identifying potential correlations between pretreatment chemistry and microbial inhibition in downstream bioconversion processes. A recently developed reversed-phase high performance liquid chromatography technique with UV detection has been applied to perform quantitative assessments of a variety of hydrolysate components as a function of pretreatment time and temperature. Correlations of product concentrations to the pretreatment severity function indicate differing responses of various compounds to the kinetic influences of temperature and reaction time. Of the compounds measured, four demonstrated initial accumulation rates were sufficiently linear over the time period tested to enable determination of activation energy E(a). All four compounds appear to demonstrate higher E(a) than that assumed in the commonly applied severity function. Overall accumulation trends for most compounds indicated similar under-estimation of apparent activation energy by the severity function. Biotechnol. Bioeng. 2007;98: 1135-1145. (c) 2007 Wiley Periodicals, Inc.

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