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MAIN CONCLUSION: Six types of lignin-carbohydrate complex (LCC) fractions were isolated from Eucalyptus. The acidic dioxane treatment applied significantly improved the yield of LCCs. The extraction conditions had a limited impact on the LCC structures and linkages. Characterization of the lignin-carbohydrate complex (LCC) structures and linkages promises to offer insight on plant cell wall chemistry. In this case, Eucalyptus LCCs were extracted by aqueous dioxane, and then precipitated sequentially by 70% ethanol, 100% ethanol, and acidic water (pH = 2). The composition and structure of the six LCC fractions obtained by selective precipitation were investigated by sugar analysis, molecular weight determination, and 2D HSQC NMR. It was found that the acidic (0.05-M HCl) dioxane treatment significantly improved the yield of LCCs (66.4% based on Klason lignin), which was higher than the neutral aqueous dioxane extraction, and the extraction condition showed limited impact on the LCC structures and linkages. In the fractionation process, the low-molecular-weight LCCs containing a high content of carbohydrates (60.3-63.2%) were first precipitated by 70% ethanol from the extractable solution. The phenyl glycoside (PhGlc) bonds (13.0-17.0 per 100Ar) and highly acetylated xylans were observed in the fractions recovered by the precipitation with 100% ethanol. On the other hand, such xylan-rich LCCs exhibited the highest frequency of ß-O-4 linkages. The benzyl ether (BE) bonds were only detected in the fractions obtained by acidic water precipitation.
Assuntos
Carboidratos/isolamento & purificação , Eucalyptus/metabolismo , Lignina/isolamento & purificação , Metabolismo dos Carboidratos , Carboidratos/química , Precipitação Química , Dioxanos/uso terapêutico , Lignina/química , Lignina/metabolismo , Espectroscopia de Ressonância Magnética , Peso MolecularRESUMO
A novel biphasic system containing water-soluble deep eutectic solvent (DES) and cyclopentyl methyl ether (CPME) was developed to treat Eucalyptus for furfural production, extracting lignin and enhancing cellulose enzymatic hydrolysis. Herein effect of DES type, water content in DES, temperature and time on furfural yield in water-soluble DES/CPME pretreatment process was firstly evaluated. A maximum furfural yield of 80.6 % was attained in 10 min at 150 °C with choline chloride (ChCl)/citric acid monohydrate (CAM)/CPME system containing 30 wt% water and 2.5 wt% SnCl4·5H2O, which was higher than that obtained from ChCl/CAM/CPME system without water (55.5 %) and H2O/CPME system (49.7 %). These results demonstrated that the water-soluble DES/CPME system was a powerful method enhancing the furfural production. Under the optimal pretreatment conditions, the delignification and glucose yield were reached to 72.7 % and 94.3 %, respectively. The extracted lignin showed low molecular weight and ß-aryl-ether was obviously cleaved. Additionally, water-soluble DES/CPME pretreatment led to a significant removal of hemicelluloses (100.0 %) and lignin (72.7 %) and introduced morphological changes on cell walls, especially from the cell corner (CC) and secondary wall (SW) layers. Overall, this work proposed a practical one-step fractionation strategy for co-producing furfural, lignin and fermentable sugar, providing a way to biorefinery.
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A facile biphasic system composed of choline chloride (ChCl)-based deep eutectic solvent (DES) and methyl isobutyl ketone (MIBK) was developed to realize the furfural production, lignin separation and preparation of fermentable glucose from Eucalyptus in one-pot. Results showed that the ChCl/1,2-propanediol/MIBK system owned the best property to convert hemicelluloses into furfural. Under the optimal conditions (MRChCl:1,2-propanediol = 1:2, raw materials:DES:MIBK ratio = 1:4:8 g/g/mL, 0.075 mol/L AlCl3·6H2O, 140 °C, and 90 min), the furfural yield and glucose yield reached 65.0 and 92.2 %, respectively. Meanwhile, the lignin with low molecular weight (1250-1930 g/mol), low polydispersity (DM = 1.25-1.53) and high purity (only 0.08-2.59 % carbohydrate content) was regenerated from the biphasic system. With the increase of pretreatment temperature, the ß-O-4, ß-ß and ß-5 linkages in the regenerated lignin were gradually broken, and the content of phenolic hydroxyl groups increased, but the content of aliphatic hydroxyl groups decreased. This research provides a new strategy for the comprehensive utilization of lignocellulose in biorefinery process.
Assuntos
Celulose , Eucalyptus , Furaldeído , Lignina , Eucalyptus/química , Eucalyptus/metabolismo , Lignina/química , Furaldeído/química , Furaldeído/análogos & derivados , Furaldeído/metabolismo , Celulose/química , Metil n-Butil Cetona/química , Metil n-Butil Cetona/metabolismo , Colina/química , Propilenoglicol/química , Glucose/metabolismo , Glucose/química , Fermentação , Solventes/químicaRESUMO
The developing of pretreatment method to break the biomass barrier of lignocellulosic is a challenging task for achieve high value utilization. A fast microwave-assisted choline chloride/1,2-propanediol/methyl isobutyl ketone biphasic system was constructed for pretreating Eucalyptus to the production of furfural and cellulose-rich residues and the extraction of lignin. Results showed that the combination of AlCl3·6H2O and HCl had the best catalytic ability for furfural production among the examined catalysts. Under the optimal conditions (140 °C, 15 min, 0.075 M AlCl3·6H2O, 0.05 M HCl), the furfural yield of 55.4 %, the glucose yield of 90.3 % and the delignification rate of 92.4 % could be achieved. Moreover, the extracted lignin samples with a low polydispersity (1.55-1.73) and molecular weight (1380-2040 g/mol) are promising to act as precursor for the value-add products processing. These findings demonstrated an ultrafast pretreatment process with excellent results in biomass fractionation and comprehensive utilization of biomass components.
Assuntos
Eucalyptus , Lignina , Lignina/química , Propilenoglicol , Furaldeído , Biomassa , Colina/química , Micro-Ondas , Solventes/química , HidróliseRESUMO
An effective approach for glucose and furfural production by converting cellulose and hemicelluloses from corn stalk in a biphasic system of molten salt hydrate (MSH) and organic solvent using H2SO4 as catalyst was reported. Results showed that the system with LiBr·3H2O and dichloromethane (DCM) had excellent performance in cellulose and hemicelluloses conversion. Under the optimal reaction conditions (corn stalk:LiBr·3H2O:DCM ratio = 0.35:10:20 g/mL/mL, 0.05 mol/L H2SO4, 120 °C, 90 min), 58.9% glucose and 72.5% furfural were yielded. Meanwhile, lignin was obviously depolymerized by the cleavage of ß-O-4' linkages and fractionated with high purity and low molecular weight for potential coproducts. Fluorescence microscopy and confocal Raman microscope displayed that the LiBr·3H2O/DCM treatment caused decreasing intensities in carbohydrate and lignin, suggesting the degradation of the main components of biomass. This research provided a promising biorefinery technology for the comprehensive utilization of corn stalk.
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Furaldeído , Lignina , Zea mays , Glucose , Solventes , Celulose , Cloreto de Sódio , BiomassaRESUMO
The alkali-soluble hemicelluloses extracted with 10% KOH solution from corn bran were further isolated with different concentrations of aqueous ethanol solutions. Herein 92.2% of the original hemicelluloses can be obtained and the cellulase enzymatic hydrolysis rate of the alkali treated corn bran can reach to 97.2%. The corn bran hemicelluloses were mainly glucuronoarabinoxylan, in which xylose (48.4-53.8%) and arabinose (27.8-33.2%) were the main components. More linear hemicelluloses with high molecular weight tended to be precipitated in low concentration aqueous ethanol solutions. Furthermore, the relationship between the structural features of these alkali-soluble corn bran hemicelluloses and their furfural yield was investigated in MIBK (methyl isobutyl ketone)/H2O biphasic system. Results showed that the hemicelluloses with high xylose content are benefit to the furfural production, and the highest furfural yield of 67.7% was obtained.
Assuntos
Furaldeído , Xilose , Álcalis/química , Etanol/química , Furaldeído/química , Hidrólise , Água/química , Zea mays/químicaRESUMO
Developing a biorefinery process for a highly integrated valorization and fractionation of lignocellulose is crucial for its utilization. Herein, a biphasic system comprising choline chloride/lactic acid and 2-methyltetrahydrofuran with Al2(SO4)3 and H2SO4 as catalysts was applied to pretreat Eucalyptus. Results showed that under the optimized conditions (150 °C, 30 min, 0.2 M Al2(SO4)3, 0.075 M H2SO4), the furfural yield and enzymatic hydrolysis efficiency could reach 54.7% and 97.0%, respectively. The efficient cellulose conversion was attributed to remarkable removal of lignin (91.0%) and hemicelluloses (100.0%), thereby causing the disruption of cell wall structure and enhancement of cellulose accessibility. Meanwhile, confocal Raman microscope and atomic force microscope displayed that the pretreatment resulted in the decreasing intensities of carbohydrates and lignin different regions of cell walls, and exposing of the embedded microfibers from noncellulosic polymers. Overall, the deep eutectic solvent-based biphasic system displayed high performance for effective utilization of carbohydrate components in lignocellulose.
Assuntos
Furaldeído , Lignina , Biomassa , Carboidratos , Celulose , Solventes Eutéticos Profundos , Hidrólise , Lignina/química , SolventesRESUMO
An aspirational pretreatment method for efficient fractionation and tailored valorization of large industrial biomass can ensure the realizability of sustainable biorefinery strategies. In this study, an ultrafast alkaline deep eutectic solvents (DES) pretreatment strategy was developed to efficiently extract the lignin nanoparticles and retain cellulose residues that could be readily enzymatic saccharified to obtain fermentative glucose for the bioenergy production from industrial xylose residue. Results showed that the DES pretreatment had excellent delignification performance and the regenerated DES lignin nanoparticles exhibited well-preserved structures and excellent antioxidant activity, as well as low molecular weights and relatively uniform size distribution, which could facilitate downstream catalytic degradation for production of chemicals and preparation of lignin-based materials. Under the optimal condition (DES pretreatment: 80 °C, 10 min; saccharification: 10 FPU/g, 5 wt%, 100 mg/g Tween 80), the glucose yield of 90.12% could be achieved, which was dramatically increased compared to raw materials.
Assuntos
Lignina , Xilose , Biomassa , Solventes Eutéticos Profundos , Glucose , Hidrólise , Lignina/química , Solventes/químicaRESUMO
BACKGROUND: Cocksfoot grass (Dactylis glomerata L.) with high biomass yield and rich cellulose can be used to produce bioethanol as fuel additive. In view of this, ultrasonic and hydrothermal pretreatments followed by successive alkali extractions were assembled into an integrated biorefinery process applied on cocksfoot grass to improve its enzymatic hydrolysis. In this work, the effects of ultrasonic and hydrothermal pretreatments followed by sequential alkali extractions on the enzymatic hydrolysis of cocksfoot grass were investigated. In addition, since large amount of hemicelluloses were released during the hydrothermal pretreatment and alkali extraction process, the yields, structural characteristics and differentials of water- and alkali-soluble hemicellulosic fractions isolated from different treatments were also comparatively explored. RESULTS: The integrated treatment significantly removed amorphous hemicelluloses and lignin, resulting in increased crystallinity of the treated residues. A maximum saccharification rate of 95.1% was obtained from the cellulose-rich substrate after the integrated treatment. In addition, the considerable hemicelluloses (31.4% water-soluble hemicelluloses and 53.4% alkali-soluble hemicelluloses) were isolated during the integrated treatment. The released water-soluble hemicellulosic fractions were found to be more branched as compared with the alkali-soluble hemicellulosic fractions and all hemicellulosic fractions were mixed polysaccharides mainly composed of branched xylans and ß-glucans. CONCLUSION: The combination of ultrasonic and hydrothermal pretreatments followed by successive alkali extractions can dramatically increase the enzymatic saccharification rate of the substrates and produce considerable amounts of hemicelluloses. Detailed information about the enzymatic hydrolysis rates of the treated substrates and the structural characteristics of the co-produced hemicelluloses will help the synergistic utilization of cellulose and hemicellulose in cocksfoot grass.
RESUMO
Herein, a two-step hydrothermal pretreatment combined with alkali extraction method was applied to deconstruct the poplar cell walls for enzymatic hydrolysis. Results revealed that 88.1 % of hemicelluloses and 77.6 % of lignin were removed during the integrated treatment performed at 180 °C and a maximum enzymatic hydrolysis efficiency of 96.1 % was achieved. Confocal Raman microscopy suggested that the removal of hemicelluloses from cell walls was inhomogeneous, and most hemicelluloses were released from the secondary wall. In addition, 35.2-56.8 % of hemicelluloses were isolated from the integrated treatment. Detailed structural analysis revealed that the water-soluble hemicelluloses possessed more branched structure than the alkali-soluble hemicelluloses and the hemicelluloses isolated from the poplar were mainly composed of a linear backbone of (1â4)-ß-d-Xylp with 4-O-Me-α-d-GlcpA attached as side chains. This work provides an efficient pathway to transform poplar into fermentable sugars and hemicelluloses with considerable yield.
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The valorization of lignin to replace phenol is significant in the production of phenolic resins. However, a great challenge is to produce lignin-based resin (LR) with a suitable viscosity and high substitution rate of lignin to phenol. In this study, LRs were produced using hardwood technical lignin derived from the pulping industry. Structural analysis of the LRs indicated that the unsubstituted para and ortho carbon atoms of the aromatic ring influenced the curing temperature and activation energy of the resins. The curing kinetics and thermal decomposition study implied that urea and methylene groups in cured LRs were significant factors that affected the thermal stability negatively. The prepared LRs showed desirable features if used as adhesives to make plywood. This is the first approach in which a substitution rate of up to 65 % is achieved for low-reactive-site hardwood lignin, which provides a solution to the challenge of the simultaneous realization of the high addition of lignin and the adaptive viscosity of resins.
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In this study, the cellulose and hemicelluloses in heartwood, sapwood, and bark of E. urophyllaâ¯×â¯E. grandis were comprehensively investigated. The ultrastructural topochemistry of carbohydrates in cell walls was examined in situ by confocal Raman microscopy. Cellulose and alkali-extractable hemicelluloses samples were isolated from different tissues and comparatively characterized by compositional carbohydrate analyses, determination of molecular weights, FT-IR spectroscopy, and XRD and NMR techniques. It was found that among all of the samples, heartwood cellulose had the highest molecular weight as well as the lowest degree of crystallinity. Meanwhile the hemicelluloses in heartwood had higher xylose content, lower degree of branching, slightly lower molecular weights but narrower polydispersity than those in sapwood. The eucalyptus hemicelluloses mainly consisted of (1â4)-ß-D-xylan backbone with glucuronic acid side chains. Furthermore, the hemicelluloses isolated from sapwood had a higher degree of substitution with terminal galactose than those isolated from heartwood and bark.
Assuntos
Parede Celular/química , Celulose/química , Eucalyptus/química , Casca de Planta/química , Polissacarídeos/química , Madeira/químicaRESUMO
Hereon, tobacco stalk was deconstructed by lyophilization, ball-milling, ultrasound-assisted alkali extraction, hydrothermal pretreatment (HTP), and alkali presoaking, respectively, followed by dilute alkali cooking to both improve its enzymatic digestibility and isolate the hemicellulosic streams. It was found that a maximum cellulose saccharification rate of 93.5% was achieved from the integrated substrate by ball-milling and dilute alkali cooking, which was 4.4-fold higher than that from the raw material. Interestingly, in this case, 76.9% of hemicelluloses were simultaneously recovered during the integrated treatment. Structural determination indicated that the hemicelluloses released from tobacco stalk by dilute alkali cooking were mixed polysaccharides, and the (1 â 4)-linked ß-D-Xylp backbone branched with L-Araf units at O-2/O-3 and 4-O-Me-α-D-GlcpA units at O-2 of the xylose residues was the main structure. In comparison, ultrasound-assisted alkali extraction, ball-milling, and HTP favored the extraction of hemicelluloses with less branched structure and lower molecular weights in the following alkali cooking.
Assuntos
Celulose , Nicotiana , Hidrólise , Peso Molecular , PolissacarídeosRESUMO
In the present study, lignin from eucalyptus was extracted with 80% alkaline dioxane (0.05 M NaOH) from ball-milled wood and subsequently fractionated by gradient acid precipitation from the filtrate. Meanwhile, the residual lignin was prepared by a double enzymatic hydrolysis process. The yield of the lignin extracted by alkaline dioxane (LA-2) was 29.5%. The carbohydrate contents and molecular weights of the gradient acid precipitated lignin fractions gradually decreased from 4.90 to 1.36% and from 7770 to 5510 g/mol, respectively, with the decline of the pH value from 6 to 2. Results from two-dimensional heteronuclear single quantum coherence nuclear magnetic resonance (NMR) and 31P NMR spectroscopy showed an evident reduction of ß- O-4 ' linkages with the pH value decrease, while the contents of aliphatic -OH, phenolic -OH, and carboxylic groups displayed an increasing trend. Moreover, the residual lignin exhibited the highest molecular weight (11690 g/mol), the most abundant ß- O-4 ' linkages (71.1%), and the highest S/G ratio (4.68).
Assuntos
Eucalyptus/química , Lignina/química , Extratos Vegetais/química , Álcalis/química , Dioxanos/química , Concentração de Íons de Hidrogênio , Hidrólise , Lignina/isolamento & purificação , Estrutura Molecular , Ressonância Magnética Nuclear Biomolecular , Extratos Vegetais/isolamento & purificação , Madeira/químicaRESUMO
Understanding the distribution and structural features of lignin in heartwood, sapwood, and bark of terrestrial plants is important to optimize the industrial utilization of lignocellulose. In this work, the lignins in heartwood, sapwood, and bark of Eucalyptus urophylla × E. grandis were comparatively studied. Confocal Raman microscopy was used to probe the heterogeneity of lignin distribution in situ. The swollen residual enzyme lignin samples were isolated and systematically characterized to determine the structural differences. The results showed that the content and molecular weights of lignin gradually decreased in the order of heartwood, sapwood, and bark. The S/G ratios of heartwood lignin (3.45) and sapwood lignin (2.74) suggested the increase of deposited S-type lignin with the maturity of wood. The bark lignin exhibited a high frequency of ß-O-4' linkages and showed a unique substructural pattern with the absence of spirodienone substructures and p-hydroxycinnamyl alcohol end-groups.
Assuntos
Eucalyptus/química , Lignina/química , Casca de Planta/química , Madeira/química , Lignina/isolamento & purificação , Estrutura Molecular , Peso Molecular , Especificidade de Órgãos , Compostos Fitoquímicos/química , Compostos Fitoquímicos/isolamento & purificação , TermogravimetriaRESUMO
An integrated process based on ionic liquids ([Bmim]Cl and [Bmim]OAc) pretreatment and successive alkali post-treatments (0.5, 2.0, and 4.0% NaOH at 90°C for 2h) was performed to isolate lignins from Eucalyptus. The structural features and spatial distribution of lignin in the Eucalyptus cell wall were investigated thoroughly. Results revealed that the ionic liquids pretreatment promoted the isolation of alkaline lignin from the pretreated samples without obvious structural changes. Additionally, the integrated process resulted in syringyl-rich lignin macromolecules with more ß-O-4' linkages and less phenolic hydroxyl groups. Confocal Raman microscopy analysis showed that the dissolution behavior of lignin was varied in the morphologically distinct regions during the successive alkali treatments, and lignin dissolved was mainly stemmed from the secondary wall regions. These results provided some useful information for understanding the mechanisms of delignification during the integrated process and enhancing the potential utilizations of lignin in future biorefineries.
Assuntos
Parede Celular/química , Eucalyptus/química , Lignina/isolamento & purificação , Álcalis/análise , Líquidos Iônicos/química , Caules de Planta/químicaRESUMO
In this work, the structural features of the lignin isolated with 2% NaOH at 90°C for 2.5h from the hydrothermally pretreated eucalyptus fibers at different temperatures (100-200°C) for different times (15-60min) were thoroughly investigated. Results showed that the hydrothermal pretreatment facilitated the separation of alkali lignin from the pretreated fibers. It was found that the linkages of ß-O-4, ß-ß, and ß-5 decreased gradually with the increase of hydrothermal severity. Furthermore, decreased molecular weights (1630-510g/mol), associated carbohydrates contents (1.99-0.05%) and aliphatic OH contents (3.37-0.65mmol/g), and increased phenolic OH contents (0.71-2.98mmol/g) and thermal stability of the alkali lignins were observed with the increase of the hydrothermal severity.
Assuntos
Eucalyptus/química , Lignina/química , Temperatura , Álcalis/química , Fracionamento Químico , Cromatografia em Gel , Estrutura Molecular , Ressonância Magnética Nuclear Biomolecular , Espectroscopia de Infravermelho com Transformada de Fourier , TermogravimetriaRESUMO
In this study, an environmental-friendly hydrothermal pretreatment of Eucalyptus fiber followed with alkali post-treatment was developed to produce bioethanol efficiently. This biorefinery process allowed all major components of biomass being converted into high value-added products. The chemical and structural features of the residual hemicelluloses isolated with alkali from the hydrothermal pretreated Eucalyptus fiber, were comparatively investigated. Sugar and spectral analyses indicated that the hemicelluloses were mainly composed of glucuronoxylans, and especially hemicelluloses prepared at higher temperature (180°C) contained higher contents of glucomannans and α-glucan. Hydrothermal pretreatment resulted in a significant hydrolysis of the glycosidic linkages in xylan backbone, and thus the molecular weight of the hemicelluloses was significantly reduced from 56,520 to 7780g/mol with the increase of temperature. This suggested that a combination of hydrothermal pretreatment at low temperatures (100-140°C) and alkali post-treatment was an effective technique for isolating of hemicelluloses from Eucalyptus fiber.
Assuntos
Eucalyptus/química , Polissacarídeos/química , Temperatura , Água/química , Fenômenos Químicos , Química Verde , Peso Molecular , Oligossacarídeos/químicaRESUMO
An environmentally friendly pretreatment process was developed to fractionate hemicelluloses from dried and water-immersed Phyllostachys pubescens chips by steam explosion followed with alkali and alkali/ethanol extractions. The detailed chemical and structural features of the isolated hemicellulosic fractions were comparatively investigated by HPAEC, GPC, FT-IR, (13)C NMR spectroscopies, and TGA analysis. It was found that the xylose/arabinose ratios of hemicelluloses obtained from alkali and alkali/ethanol extractions were 21.5-34.4 and 7.7-9.9, respectively, suggesting that hemicelluloses extracted with alkali had relatively lower degree of branches than those extracted with alkali/ethanol. Hemicellulosic fractions isolated from the water-immersed samples were obtained in high yields and exhibited similar compositions, which can be used as raw materials for production of value-added products. Furthermore, the hemicelluloses extracted with alkali had relatively higher molecular weight than those extracted with alkali/ethanol. In addition, an increment of incubation time resulted in a decreased thermal stability of hemicelluloses obtained from water-immersed sample.
Assuntos
Poaceae/química , Polissacarídeos/química , Vapor , Concentração de Íons de Hidrogênio , Peso Molecular , Temperatura , Ácidos Urônicos/análiseRESUMO
An environmentally friendly steam explosion process of bamboo, followed by alkali and alkaline ethanol delignification, was developed to fractionate lignins. Results showed that after steam explosion the lignins isolated showed relatively low carbohydrate contents (0.55-1.76%) and molecular weights (780-1050 g/mol). For each steam-exploded sample, alkali-extracted lignins presented higher phenolic OH values (1.41-1.82 mmol/g), p-coumaric acid to ferulic acid ratios (pCA/FA ratios 4.5-14.1), and syringyl to guaiacyl ratios (S/G ratios 5.0-8.5) than those from alkaline ethanol-extracted lignins (phenolic OH 0.85-1.35 mmol/g, pCA/FA ratios 1.6-5.2, and S/G ratios 3.5-4.8). The lignins obtained consisted mainly of ß-O-4' linkages combined with small amounts of ß-ß', ß-5', and α-O-4/ß-O-4 linkages. Antioxidant activities of the lignins obtained were tested by the 2,2-diphenyl-1-picrylhydrazyl, 2,2'-azobis(3-ethylbenzothiazoline-6-sulfonic acid), and ferric reducing activity power methods. It was found that alkali-extracted lignins obtained during the initial extraction process had higher antioxidant activities than alkaline ethanol-extracted lignins obtained during the second extraction process.