Bioresource Technology 98 (2007) 19511957

Autohydrolysis of agricultural residues: Study of reaction byproducts

Gil Garrote a, Elena Falqu b, Herminia Domnguez a, Juan Carlos Paraj
a b

a,

Department of Chemical Engineering, Faculty of Science, University of Vigo (Campus Ourense), As Lagoas, s/n. 32004 Ourense, Spain Department of Analytical Chemistry and Food Science, Faculty of Science, University of Vigo (Campus Ourense), As Lagoas, s/n. 32004 Ourense, Spain Received 19 June 2006; received in revised form 20 July 2006; accepted 22 July 2006 Available online 6 October 2006

Abstract Samples of rice husks and corn cobs were subjected to hydrothermal treatments in aqueous media under conditions leading to maximal xylooligomer concentration, and the reaction liquors were extracted with dichloromethane (DCM) to assess the type and amount of reaction byproducts with potential application as food ingredients and cosmetics. The identiWed DCM-soluble compounds were classiWed in four categories (sugar-derived compounds, lignin-derived compounds, nitrogen-containing compounds and fatty acids). The experimental results were compared with literature data. 2006 Published by Elsevier Ltd.
Keywords: Autohydrolysis; Byproducts; Corn cobs; Hydrothermal treatments; Rice husks

1. Introduction Treatments of lignocellulosic materials (LCM) in aqueous media (autohydrolysis or hydrothermal treatments) under optimized conditions lead to the solubilisation of hemicelluloses, leaving a solid phase enriched in both cellulose and lignin (Garrote et al., 1999). This solid phase can be subjected to further processing for obtaining a variety of commercial products, for example enzymatic hydrolysis and further fermentation of hydrolyzates, (Lasser et al., 2001; Rivas et al., 2004), allowing an integrated beneWt of the raw material. The hemicellulosic fraction of LCM accounts usually for 1450% of the raw material dry weight, and is made up of amorphous heteropolysaccharides containing diVerent structural units (including xylose, arabinose, mannose, galactose or rhamnose), which can be substituted with phenolic, uronic or acetyl groups. Xylan (made up of a main backbone of xylose units) is the main hemicellulose component in hardwoods and many agricultural products (including corncobs and rice husks). Arabinose substituents and esteriWed ferulic acid (Parker et al., 2000, 2005) or more
*

Corresponding author. E-mail address: jcparajo@uvigo.es (J.C. Paraj).

complex phenolic compounds as dimmers or trimmers (Bunzel et al., 2005) can be present in this type of materials, binding lignin with polysaccharides (Pan et al., 2002). When autohydrolysis of a xylan-containing LCM is carried out under suitable operational conditions, the major reaction products are substituted xylooligomers (SXO), which have food and pharmaceutical applications (Vzquez et al., 2001). Considered as food additives, SXO have prebiotic properties (Fooks and Gibson, 2002; Rycroft et al., 2001), derived from their preferential utilization by BiWdobacteria (Izumi and Kojo, 2003) and ability for inhibiting the growth of Clostridium (Izumi and Azumi, 2001). In the autohydrolysis media, SXO can be hydrolyzed to sugars, which can be decomposed (Garrote et al., 2004a). On the other hand, acetyl groups are partially saponiWed, extractives are removed from the solid phase, a part of ashes are dissolved, compounds belonging to the acid-soluble lignin fraction are extracted and proteins may react with sugars to give Maillard Reaction Products. Because of these side eVects, the compositions of autohydrolysis media are complex and SXO must be reWned before application. ReWning of liquors has been carried out by solvent extraction and other separation operations (Vzquez et al., 2001). The interest in performing a solvent extraction stage of SXO-containing autohydrolysis liquors lies in the following

0960-8524/$ - see front matter 2006 Published by Elsevier Ltd. doi:10.1016/j.biortech.2006.07.049

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G. Garrote et al. / Bioresource Technology 98 (2007) 19511957

points: (i) compounds derived from extractives and acidsoluble lignin can be removed from the media; (ii) the separation can be carried out without signiWcant losses of SXO; (iii) the solvent-soluble fractions have antioxidant and antimicrobial activities, which make them potentially suitable for food or cosmetic application (Garrote et al., 2004b, Moure et al., 2001). This work deals with the identiWcation and quantiWcation of reaction products from hydrothermal processing of corn cobs and rice husks, a basic information for assessing further puriWcation processes and developing possible applications of the extracted fractions. 2. Methods 2.1. Materials Rice husks (supplied by Procesadora Gallega de Alimentos, Laln, Pontevedra, Spain) and locally collected corncobs were air-dried. Corncobs were milled to pass a 1 mm screen. Homogenised lots of milled corncobs and rice husks were prepared to avoid diVerences in composition among aliquots, and stored. Aliquots from the above homogenised lots were subjected to moisture determination (TAPPI standard T-264-om-88) and to conventional quantitative acid hydrolysis with 72% H2SO4. The solid residue after hydrolysis was considered as Klason lignin after correction for ashes. Hydrolysates were analyzed for monosaccharides (glucose coming from cellulose; xylose and arabinose coming from hemicelluloses) and acetic acid (coming from acetyl groups) by HPLC as reported elsewhere (Garrote et al., 1999). Uronic acids were determined spectrophotometrically (Blumenkrantz and Asboe-Hansen, 1973) using galacturonic acid as a standard for quantiWcation. Proteins were determined from the nitrogen content of samples, which was measured by elemental analysis (Flash 1112 Series, Termo Finningan). Ashes were determined by calcination (TAPPI standard T-244-om-93). 2.2. Autohydrolysis Lignocellulosic materials were contacted with water in a batch stainless steel reactor of 3.75 L (Parr Instruments Company, Moline, Illinois) with temperature control using a liquid/solid ratio of 8:1 kg/kg and heated to the desired temperature following the standard temperature proWle of the reactor. The Wnal temperatures leading to optimal SXO concentrations were 205 C for rice husks (Vila et al., 2002) and 202 C for corncobs (Garrote et al., 2002). Solid and liquid phases were separated by Wltration. The solid residue was washed, dried and used to measure the solid yield. Aliquots of the liquid phase were oven-dried at 105 C to constant weight to measure the content of non-volatile components (NVC). Samples of liquors from hydrothermal treatments were Wltered through 0.45 m membranes and used for direct HPLC determination of glucose, xylose, arabinose, 5-hydroxy-2-methylfurfural (HMF), furfural,

and acetic acid, using IR detection for determination of glucose, xylose, arabinose and acetic acid, and DAD detection for determination of furfural and HMF. Analysis were performed with a Biorad Aminex HPX-87H column eluted with 0.003 M H2SO4. A second sample of liquors was subjected to quantitative posthydrolysis (with 4% H2SO4 at 121 C for 40 min) before HPLC analysis and uronic acid determination. The increase in the concentrations of monosaccharides and acetic acid caused by posthydrolysis provided a measure of the oligomer concentration. 2.3. Extraction Liquors (150 mL) were treated with dichloromethane (DCM) in three-stage, crossXow extraction (employing 15, 7.5 and 7.5 mL in the respective stages), with 5 min of contact time and magnetic stirring at 600 rpm, and intermediate periods of 5 min for phase separation. The organic phases were mixed and concentrated under N2 prior analysis. 2.4. Gas chromatographymass spectrometic analysis GCMS was performed using a Hewlett-Packard 5890II gas chromatograph coupled to a mass spectrometer HP5970 using He as carrier gas (125,000 Pa). Analyses were carried out in splitless mode. Separation was performed using a 60 m 0.25 mm 0.25 m Wlm thickness HP-Innowax capillary column. Temperature was kept at 45 C for 1 min, programmed to 230 C at 3 C/min, and then held for 30 min. Mass spectrometer was in EI mode (electron energy 70 eV; source temperature 250 C), and data acquisition was made in scanning mode from 30 to 300 amu/s and 1.9 spectra/s. Compounds were identiWed by comparison of the retention time and mass spectra with library data of mass spectra and authentic compounds. Quantitation was performed by the internal standard method (using 3-octanol and 3,4-dimethylphenol as standards) using model compounds for calibration. 3. Results and discussion 3.1. Composition of raw materials and liquors Tables 1 and 2 show the composition of raw materials and liquors, as well as the standard deviation of data (based on six replicate determinations). The raw materials are deWned by their contents of glucan (corresponding to cellulose), xylan (measured as xylose equivalent, which form the main polymer backbone), xylan substituents (arabinose units, reported as arabinan expressed in sugar equivalent, and acetyl groups), lignin, ash, protein and other components. Xylan and xylan substituents accounted jointly for 20.0 and 40.6 wt% of rice husks and corncobs (in oven-dry basis). Autohydrolysis caused a substantial solubilisation of the feedstocks (21.0 and 36.2 o.d. wt% of rice husks and corncobs, respectively), yielding volatile components (mainly ace-

G. Garrote et al. / Bioresource Technology 98 (2007) 19511957 Table 1 Compositional data of raw materials (wt%, oven-dry basis) Fraction Glucan (cellulose) Xylan Arabinan Acetyl groups Uronic acids Lignin Ash Protein Others (by diVerence) Rice husks (% o.d. weight) 36.7 15.6 1.68 1.62 1.14 21.3 14.3 2.50 5.16 SDa 0.74 0.12 0.01 0.14 0.17 0.08 0.09 0.09 Corn cobs (% o.d. weight) 34.3 31.1 3.01 3.07 3.45 18.8 1.30 3.25 1.72 SDa 0.53 0.45 0.40 0.01 0.31 0.21 0.05 0.12

1953

compounds. As expected, SXO (calculated as the sum of XO and XO substituents) were the main reaction products, accounting for 65.9% and 67.7% of NVC for rice husks and corn cobs. 3.2. Analysis of DCM-soluble compounds Solvent extraction has been frequently used to fractionate reaction liquors. Karagz et al. (2004, 2006) extracted acidiWed autohydrolysis liquors from pine sawdust (treatment conditions, 180 C and 280 C) with diethyl ether, obtaining yields of 0.8% and 1.3% g soluble material/100 g o.d. sawdust, whereas Sun et al. (2003) achieved 0.56 g material soluble in DCM/100 g o.d. substrate in the liquid phase from water treatments of wheat straw (performed at 95 C). In this work, the yields of DCM-soluble material were 0.322 and 0.514 g/100 g o.d. feedstock for rice husks and corncobs, respectively. In related studies, the direct extraction of lignocellulosic raw materials with DCM has been considered. Yields of 0.26, 0.44, 0.45 and 1.17 g/100 g o.d. raw material have been reported for Eucalyptus wood (Gutirrez et al., 1999; Freire et al., 2002a), Eucalyptus bark (Freire et al., 2002b), rice straw (Xiao et al., 2001) and wheat straw (Sun et al., 2003). To our knowledge, no detailed studies have been reported on the quantiWcation of autohydrolysis reaction byproducts. IdentiWcation of compounds from this type of media has been reported for treatments of pine sawdust, hinoki bark, cellulose and wheat straw (Ehara and Saka, 2005; Karagz et al., 2004; Quitain et al., 2003; Sun et al., 2003). Related studies have been published for aqueous treatments in catalyzed media, usually at temperatures in the range 280400 C. This information refers to media catalyzed with RbOH and CsOH (Karagz et al., 2005), K2O3 (Karagz et al., 2006), Na2CO3 (Klinke et al., 2002), NaOH (Taner et al., 2004), acetic acid (Taner et al., 2004) and HNO3 (Luo et al., 2002), but the distribution of products was strongly modiWed by the presence of catalysts. Fig. 1a and b shows the results obtained in the GCMS analysis of the DCM-soluble fraction of liquors from hydrothermal treatments of corn cobs and rice husks, and Table 3 lists data concerning the respective compositional analysis. In order to allow an easier discussion of results, the compounds in Table 3 have been classiWed in to four groups: sugar-derived compounds (SDC), lignin-derived compounds (LDC), nitrogen-containing compounds (NCC) and fatty acids (FA). SDC accounted for 35.0 and 32.3 wt% of total mass identiWed in samples from corn cobs and rice husks, respectively. Furfural was the main compound belonging to this group, in amounts of 887.1 and 456.3 mg/kg for corncobs and rice husks; which corresponded to 83.3 and 76.7 wt% of the respective SDC fractions. Furfural (mainly from pentose dehydration in acidic media) has been found in related studies (Ciccioli et al., 2001; Guilln and Manzanos, 1999, 2002; Karagz et al., 2004, 2005, 2006; Klinke et al., 2002; Quitain et al., 2003) and in studies with pure sugars

Results have been calculated from six replicate determinations. a SD D standard deviation. Table 2 Compositional data of raw liquors (expressed weight percent of untreated, oven-dry raw material) Rice husks (% o.d. weight) Average Dissolved solidb 21.03 Non-volatile compounds 19.63 (NVC) Volatile compounds 1.40 (VC, by diVerence) Volatile compounds identiWed Acetic acid 0.64 HMF 0.03 Furfural 0.26 Non-volatile compounds identiWed Arabinose 0.61 Glucose 0.79 Xylose 0.98 Gluco-oligosaccharides (GO) 2.23 Xylo-oligosaccharides (XO) 9.16 Arabino-oligosaccharides 0.36 (ArO) Acetyl groups0.38 oligosaccharides (AcO) Uronic acids 0.81 Others (by diVerence) 3.38 SDa 0.071 0.043 Corn cobs (% o.d. weight) Average 36.19 34.59 1.60 SDa 0.085 0.099

0.011 0.001 0.011

0.48 0.10 0.47

0.008 0.002 0.011

0.024 0.034 0.044 0.054 0.121 0.007 0.008 0.041

1.14 0.47 2.17 0.49 18.29 1.01 1.51 2.13 6.33

0.024 0.005 0.044 0.005 0.211 0.019 0.021 0.106

Results have been calculated from six replicate determinations. a SD D standard deviation. b Dissolved solid calculated as 100 solid yield.

tic acid, furfural and HMF, but also volatile extractives not identiWed) and non-volatile components (NVC). NVC are made up of monosaccharides (glucose, xylose and arabinose), oligosaccharides (glucooligosaccharides GO, xylooligosaccharides XO and arabinooligosaccharides ArO, used to quantify the arabinose units linked to oligosaccharides), acetyl groups linked to oligosaccharides (AcO) and a fraction denoted others, calculated by diVerence respect to the total NVC content, which included uronic substituents of oligosaccharides and non-saccharide components, including proteins and protein-reaction products, phenolic compounds derived from the acid-soluble lignin fraction, dissolved in-organic components and extractive-derived

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G. Garrote et al. / Bioresource Technology 98 (2007) 19511957

Fig. 1. GCMS chromatograms of the dichloromethane soluble of hydrothermal liquors from (a) corncobs, (b) rice husks. Numbers of peaks correspond to the compounds listed in Table 3.

(Srokol et al., 2004). In our work, 5-hydroxy-2-methylfurfural was determined in liquors (see Table 2), but it was not detected in DCM-soluble fractions. Other reported sugardegradation products obtained under harsh conditions (including pyruvaldehyde, levoglucosan or erythrose), whose occurrence has been reported (Sasaki et al., 1998; Ehara and Saka, 2005), did not appear in the analyzed fractions, probably owing to the comparative low severity of hydrothermal treatments carried out in this work. Additional compounds of this group, including 2,5-hexane-dione, 5methylfurfural, or cyclotene, already identiWed by Karagz et al. (2004, 2005, 2006) in autohydrolysis media, were found and quantiWed in this work (see Table 3). Other major compounds found in the analysed fractions were 5-methylfurfural (in amounts corresponding to 10.4% and 16.2% of SDC for corn cobs rice husks, respectively), 4,5-dimethylfurfural (in amounts corresponding to 1.9% and 2.0% of SDC for the same samples) and 2-acetylfuran (accounting for 1.2 and 1.8 of SDC for the respective samples). Compounds such as 2-acetylfuran, 2,5-hexanedione, 5-methylfurfural, -butyrolactone, furfuryl alcohol, -valerolactone, dihydropyran or cyclotene, whose presence in LCM combustion smokes has been reported in literature (Ciccioli et al., 2001; Fine et al., 2004; Guilln et al., 1999, 2002) have been found in the DCM soluble fraction of autohydrolysis liquors from corn cobs and rice husks (see Table 3). 2-Acetylfuran, 2,5-hexanedione, 5-methylfurfural or furfuryl

alcohol have been reported to be also generated from melanoidin decomposition (Adams et al., 2003, 2005), whereas autohydrolysis of glucose-glycine mixtures leads to the formation of cyclotene and lactones (Inoue et al., 2004). LDC fractions were obtained at yields of 1799.9 mg/kg from corn cobs and 1111.0 mg/kg from rice husks, corresponding to 59.2 and 60.4 wt% of the total mass identiWed for the respective substrates. Thirty aromatic compounds have been identiWed in the LDC fraction, the major ones being vanillin (accounting for 36.3 and 19.5 wt% of the LDC fractions obtained from corn cobs and rice husks, respectively), 4-vinylphenol (accounting for 13.8 wt% of LDC for both raw materials), 4-vinylguaiacol (16.1 and 8.1 wt% of LDC from corn cobs and rice husks, respectively), syringaldehyde (accounting for 8.0 and 8.7 wt% of LDC from the respective feedstocks) and 4-hydroxy-2methoxycinnamaldehyde (accounting for 4.4 and 12.2 wt% of LDC from the respective feedstocks). 3-methylphenol was the major LDC component in pine sawdust autohydrolysis media, followed by guaiacol, homovanillic alcohol, 4ethylguaiacol, catechol, 4-methylguaiacol and phenol (Karagz et al., 2006). Klinke et al. (2002) found a wide variety of phenolic compounds in the alkaline wet oxidation of wheat straw, being vanillic acid and vanillin the major components, followed by 4-hydroxybenzaldehyde, syringaldehyde, syringic acid, coumaric acid and guaiacol. Autohydrolysis treatments of wheat straw carried under mild conditions (Sun et al., 2003) led to a related distribution of phenolic compounds, the most important being syringaldehyde, cinnamic acid, vanillic acid and vanillin, but at a much lower yield. Other compounds quantiWed in this work (including guaiacol, 4-ethylguaiacol, eugenol, 4-vinylguaiacol, syringol, isoeugenol, vanillin, acetovanillone, guaiacylacetone, methoxyeugenol, syringaldehyde, homovanillic acid and acetosyringone) were identiWed in liquors from wood treatments with supercritical water at 380 C for 8 s (Ehara et al., 2005; Takada et al., 2004); whereas guaiacol, 2,4-ditertbutylphenol and 1,3-ditertbutylbenzene have been found in autohydrolysis liquors from hinoki bark (Quitain et al., 2003). A variety of phenolic compounds have been identiWed in samples from rice and corn, some of them also found in this work: for example, Jezussek et al. (2002) found vanillin, guaiacol, 4-vinyl-guaiacol and 4-vinyl-phenol in simples of brown rice, whereas Fontaine et al. (2003) identiWed vanillin, 4-ethylphenol, 4-methylguaiacol, 4-vinylguaiacol, 4-vinylphenol, syringol, eugenol, guaiacylacetone, methoxyeugenol, syringaldehyde, coniferyl alcohol and acetosyringone in neutral detergent Wbre from corn. NCC were found in limited amounts (1.1% and 1.3% of total DCM soluble fraction from corncobs and rice husks, respectively). The major NCC were 1-pyrrol-2-carboxaldehyde and methylpyrrolecarboxaldehyde. Related structures have been reported to be present in aqueous media containing melanoidins from reactions of glucose and glycine (Inoue et al., 2004; Adams et al., 2003, 2005), as well as in roasted earth almond (Cantalejo, 1997).

G. Garrote et al. / Bioresource Technology 98 (2007) 19511957 Table 3 Composition of the DCM-soluble fractions from corn cobs and rice husks (expressed as mg/kg of oven-dry raw material)
No. t (min) Name Corn cobs Average Sugar derived compounds 1 22,72 2 23,80 3 23,93 5 26,51 7 27,96 8 28,46 10 29,43 11 30,52 12 32,62 16 35,68 20 38,39 Lignin derived compounds 4 24,50 9 29,20 14 33,90 15 35,43 18 36,59 19 37,15 23 41,46 25 42,30 27 46,52 28 46,75 30 47,12 31 47,56 32 48,25 34 49,50 35 51,09 36 51,90 37 52,94 39 58,16 40 58,70 41 59,73 42 60,18 43 61,55 44 61,98 47 68,17 48 68,23 49 69,16 50 69,90 51 70,39 52 70,74 53 76,78 Nitrogen-containing compounds 6 27,49 22 40,29 24 41,90 33 48,39 Fatty acids 13 17 21 26 29 45 46 54 55 56 Furfural 2-Acetylfuran 2,5-Hexanedione 5-Methylfurfural 4,5-Dimethylfurfural -Butyrolactone Furfuryl alcohol -Valerolactone Dihydropyran Cyclotene Furfural acetone 1065.1 887.1 12.8 5.0 111.1 20.6 3.6 6.3 5.2 5.2 4.4 3.8 1799.9 7.0 9.3 10.8 10.4 48.2 7.7 19.9 6.4 3.3 9.5 289.8 9.6 32.5 22.5 15.8 248.0 653.2 13.7 80.8 12.1 7.4 6.6 144.7 SDa 13.7 0.7 <0.05 1.9 0.5 <0.05 1.0 0.3 <0.05 0.1 <0.05 Rice husks Average 595.2 456.3 10.8 2.9 96.3 12.0 4.1 3.0 3.9 5.9 SDa 1.6 1.7 0.5 1.4 0.4 0.3 0.1 0.5 0.2

1955

Benzaldehyde Benzeneacetaldehyde Acetophenone 3,5-Dimethylbenzaldehyde Guaiacol Benzyl alcohol Phenol 4-Ethylguaiacol 4-Eugenol 4-Ethylphenol 2,3-Dihydroxybenzaldehyde 4-Vinylguaiacol 2,5-Dihydroxyacetophenone Syringol 2,4-Ditertbutylphenol Isoeugenol 4-Vinylphenol Vanillin Homovanillyl alcohol Acetovanillone Guaiacylacetone Methoxyeugenol Coniferyl alcohol Syringaldehyde 4-Hydroxybenzaldehyde Homovanillic acid Acetosyringone Acetylphenol 1-(2,6-Dihydroxy-4-methoxyphenyl)-ethanone 4-Hydroxy-2-methoxycinnamaldehyde

0.7 0.3 0.1 0.6 0.3 0.1 0.3 0.1 0.5 0.7 7.2 0.5 2.5 1.5 1.2 5.3 40.8 1.1 3.1 1.1 0.2 <0.05 7.7

1111.0 3.8 3.6 1.4 4.7 44.0 13.0 5.6 2.5 3.4 89.6 30.7 16.6 18.8 153.4 216.7 7.6 73.6 62.0 20.5 96.9 12.9 41.2 45.6 6.9 136.1 23.1 2.5 3.9 7.1 9.7 111.1 4.0 17.7 2.9 5.4 3.9 6.8 27.9 23.8 13.5 5.2

0.8 0.2 0.4 <0.05 2.4 1.2 0.4 0.1 <0.05 4.3 2.4 1.0 0.5 19.3 11.4 0.5 1.2 4.2 0.3 5.1 <0.05 0.9 5.1 0.1 8.6

25.1 8.2 18.1 79.2 34.3 4.7 17.4 12.2 142.9

0.9 0.3 1.8 1.6

2-Acetylpyridine 2-Acetylpyrrol 1-Pyrrol-2-carboxaldehyde Methylpyrrolecarboxaldehyde

0.6 2.1 0.1

0.1 0.1 0.6 0.3

32,70 36,35 39,98 43,48 46,89 62,09 67,60 77,23 78,52 81,47

Pentanoic acid (valeric acid) Hexanoic acid (caproic acid) Heptanoic acid (enanthic acid) Octanoic acid (caprylic acid) Nonanoic acid (pelargonic acid, 9:0) Tetradecanoic acid (myristic acid, 14:0) Hexadecanoic acid (palmitic acid, 16:0) Octadecanoic acid (stearic acid, 18:0) 9-Octadecenoic acid (oleic acid, 18:1) 9,12-Octadecanedioic acid (linoleic acid, 18:2)

9.0 5.1 2.7 2.5 28.4 40.3 30.0 13.0 11.7

0.7 0.6 <0.05 <0.05 2.3 0.8 1.7 0.6 <0.05

<0.05 0.9 0.2 0.4 0.2 0.3 2.3 <0.05 1.0 0.5

Results have been calculated from three replicate determinations. a SD D standard deviation.

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G. Garrote et al. / Bioresource Technology 98 (2007) 19511957

The contents of FA in samples from corn cobs and rice husks accounted for 142.9 mg/kg and 111.1 mg/kg, respectively, corresponding to 4.7 and 6.0 wt% of the DCM-soluble material. FA make part of LCM, and their content has been recently studied for a variety of feedstocks, including Eucalyptus wood (Gutirrez et al., 1999; Freire et al., 2002a), yellow birch (Lavoie and Stevanovic, 2005), Xax (Gutirrez and del Ro, 2003; Morrison and Akin, 2001) or barks (Freire et al., 2002b, HaWzoflu et al., 2002). Even though the total amount of FA and the relative proportions of individual compounds vary in a wide range with the source studied, the most abundant FA have chains with more than 14 carbon atoms, and particularly chains of 18 carbon atoms (for example, octadecanoic, 9-octadecenoic and 9,12-octadecanedioic acids). Tetradecanoic, 9-octadecenoic and 9,12octadecanedioic acids also appear in important proportions. In related studies with other LCM, the predominant FA have been reported to be octadecanoic and hexadecanoic acids (Quitain et al., 2003) and heneicosanoic and hexadecanoic acids (Sun et al., 2003). Saturated fatty acids with chains of 5, 6, 7, 8 and 9 carbon atoms have been found in this work, accounting for 13.6% and 30.5% of total FA in corncobs and rice husks. As these compounds do not appear in the DCM extractives of the untreated LCM, they must have been generated by hydrolytic reactions during the hydrothermal processing. This same compounds have been detected in smokes from Pinus pinea and wheat straw (Ciccioli et al., 2001), sage and oak (Guilln et al., 1999, 2002) and woods (including white oak, red maple, sugar maple, douglas Wr and loblolly pine) (Fine et al., 2004). 4. Conclusions Autohydrolysis liquors from rice husk and corn cob processing were extracted with dichloromethane (DCM). The yields in soluble material were 0.322 and 0.514 g/100 g oven dry feedstock for rice husks and corncobs, respectively. The identiWed compounds were classiWed in four groups: sugarderived compounds (SDC), lignin-derived compounds (LDC), nitrogen-containing compounds (NCC) and fatty acids (FA). SDC accounted for 35.0 and 32.3 wt% of total mass identiWed in samples from corn cobs and rice husks, respectively. LDC corresponding to 59.2 and 60.4 wt% of the total mass were identiWed in samples from corn cobs and rice husks, respectively. NCC were found in limited amounts (1.1% and 1.3% of total DCM soluble fraction from corncobs and rice husks, respectively). The contents of FA in samples from corn cobs and rice husks accounted for 4.7 and 6.0 wt% of the DCM-soluble material from corncobs and rice husks, respectively. Furfural was the most abundant compound, followed by vanillin, 4-methylphenol and 4-vinylguaiacol. Acknowledgements Authors are grateful to the Spanish Ministry of Science of Technology for the Wnancial support of this work (in the

framework of the Research Project Development of technologies for the integral beneWt of industrial byproducts, Ref. CTQ2005-00745), which had partial Wnancial support from the FEDER funds of the European Union. Dr. Gil Garrote is a researched hired by the Ramn y Cajal Program of the Spanish Ministry of Education and Science. References
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