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Cellulose 10: 325334, 2003. # 2003 Kluwer Academic Publishers. Printed in the Netherlands.

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Molecular properties of hemicelluloses located in the surface and inner layers of hardwood and softwood pulps
Olof Dahlman*, Anna Jacobs and John Sjo berg

Swedish Pulp and Paper Research Institute, Box 5604, SE-114 86 Stockholm, Sweden; *Author for correspondence (e-mail: olof.dahlman@stfi.se; fax: +46-8-108340)
Received 21 November 2002; accepted in revised form 9 April 2003

Key words: Bleached pulps, Carbohydrates, Fiber fractions, Hemicellulose, Kraft pulps, Molar mass, Molecular properties, Surface properties, Uronic acids, Xylans Abstract The molecular properties of hemicelluloses located in the surface and inner layers of fibers present in hardwood and softwood pulps, together with the effects of different bleaching processes on these properties, have been investigated in this study. In order to separate the hemicelluloses located in these two layers, fibers were subjected to mechanical peeling and then separated by filtration into surface (filtrate) and inner layer materials. The materials thus obtained were characterized with respect to their polysaccharide compositions and uronic acid contents. The molar mass parameters of the hemicelluloses (extracted by alkali) were determined by employing size-exclusion chromatography in combination with off-line MALDI mass spectrometry. For all of the pulps examined, the relative content of xylan was found to be greater in the surface layer of the fiber than in the corresponding inner layer. The xylan polymers of the surface layer exhibited higher molar masses and lower frequencies of uronic acid side groups than did the xylans in the inner fiber layer. In connection with ozone treatment, hexenuronic acid residues in the surface layer xylan were removed to a greater extent than in the case of the inner layers, indicating a gradient for the reaction with ozone across the fiber wall. The xylan polymer remaining on the surface of the softwood pulps after completion of the chlorine dioxide bleaching process was predominantly uncharged. Abbreviations: CE Capillary electrophoresis; ECF Elementary chlorine-free; HexA Hexenuronic acid (4-deoxy-L-threo-hex-4-eno-pyranosyluronic acid); MALDI-MS Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry; MeGlcA 4-O-Methylglucuronic acid; Mn Number-average molar mass; Mw Weight-average molar mass; Mw/Mn Polydispersity index; SEC Size-exclusion chromatography; TCF Totally chlorine-free.

Introduction The major components of the secondary layers of the cell wall in wood fibers are cellulose and various heteropolysaccharides, referred to as hemicelluloses (Meier 1961, 1985; Timell 1967). Although less abundant than cellulose, these hemicelluloses

contribute significantly to the mechanical strength of delignified wood fibers and papers made from such fibers (Leopold and McIntosh 1961; Pettersson and Rydholm 1961; Spiegelberg 1966; Kettunen et al. 1982). This is especially true in the case of the hemicelluloses present in the surface layer (Mobarak et al. 1973; Bachner et al. 1993;

326 Scho nberg et al. 2001), i.e., the outer layer of the fibers, where these polymers can act as adhesives to strengthen the bonds between individual fibers in the three-dimensional network of a sheet of paper. The solubility, adsorption behavior and strength of hemicellulose polymers are influenced to various degrees by the neutral monosaccharide and uronic acid residues they contain, as well as by the frequency of side chain substituent sugar residues and their molar mass parameters (Wikstro m 1968; dkova and Ebringerova Whistler 1973; Hroma 1993). Therefore, as correctly pointed out as long as four decades ago by Von Koeppen (1964), information concerning the quantity and distribution of the hemicelluloses present in the fiber wall, together with their molecular properties (e.g., composition, frequency of side groups and molar mass parameters) is required in order to understand the factors responsible for the often pronounced variations in the papermaking properties of pulps obtained employing different pulping processes. Despite this realization, only few studies on the molecular properties of hemicelluloses present in the surface layers of wood pulps have been reported. Two such investigations examined the radial distributions of polysaccharides with different molecular characteristics in softwood kraft and sulfite pulps, employing a chemical peeling method involving selective derivatization (acetylation) of the polysaccharides in the outer fiber layer and subsequent extraction of these derivatized polysaccharides (Luce 1964; Bachner et al. 1993). However, this approach only allows determination of the properties (e.g., degree of polymerization) of the entire polysaccharide mixture, containing both cellulose and hemicelluloses derivatives, and consequently does not provide information concerning the molar masses of hemicelluloses located in the surface layers. Mechanical peeling is an alternative approach that has been utilized for the isolation of materials in the surface and inner layers of fibers from different types of chemical pulps (Kallmes 1960; Purina et al. 1994; Heijnesson et al. 1995; Sjo berg et al. 2002). This approach involves the application of sheer forces to the fibers by gentle mechanical agitation in a disintegrator, which peels off surface layer materials from the fibers. The material removed and the remaining fibers thus obtained can subsequently be characterized separately employing modern analytical procedures (Kleen et al. 2002; Sjo berg et al. 2002). The objective of the present study was to examine the molecular properties of hemicelluloses present in the surface layers of softwood and hardwood kraft fibers, as well as to examine the effects of different bleaching processes on these properties. For this purpose, mechanical peeling was employed to isolate surface and inner layer material from pulp samples collected along the production lines in two kraft pulp mills utilizing oxygen delignification followed by chlorine dioxide (ECF) or alkaline peroxide and ozone (TCF) bleaching sequences. Thereafter, enzymatic hydrolysis and capillary electrophoresis (Dahlman et al. 2000) were utilized to determine the polysaccharide compositions and uronic acid contents of the materials obtained. A procedure involving size-exclusion chromatography followed by off-line matrixassisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-MS) was applied to obtain the molar mass parameters (Jacobs and Dahlman 2001a) of the hemicelluloses. Materials and methods Materials Samples of hardwood kraft pulps were collected at different points along the production line in a mill utilizing continuous kraft cooking, oxygen delignification and TCF bleaching involving a combination of treatments with alkaline peroxide and ozone (these samples are denoted HK-U, HK-O, and HK-TCF). The samples of softwood kraft pulps originated from a mill carrying out batch cooking, oxygen delignification and ECF bleaching by sequential treatment with chlorine dioxide and alkaline peroxide (samples SK-U, SK-O, and SK-ECF). Finally, a sample of an unbleached hardwood sulfite pulp (HS-U), used for comparison, was obtained from a mill employing a magnefite cooking process. Table 1 documents the pulping process, kappa number and contents of lignin and hexenuronic acid residues (HexA) for these different samples. The unbleached and oxygen-delignified pulp samples were kept frozen, while the fully bleached pulps were stored as dried sheets at 2023  C until use. Prior to mechanical

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Table 1. The pulping process, kappa number and lignin and hexenuronic acid (HexA) contents of the unbleached and bleached hardwood and softwood chemical pulps. Samples Hardwood pulps HK-U (unbleached kraft pulp) HK-O (oxygen bleached kraft pulp) HK-TCF (ozone/peroxide-bleached kraft pulp) HS-U (unbleached sulfite pulp) Softwood pulps SK-U (unbleached kraft pulp) SK-O (oxygen bleached kraft pulp) SK-ECF (chlorine dioxide bleached kraft pulp) NA not analyzed. Pulping process Kappa number 13.6 10.7 3.3 16.4 19.1 9.9 0.8 Lignin (mass %) 1.9 1.2 0.8 NA NA NA NA HexA (mmol/kg) 75 75 34 <3 31 31 4

Continuous kraft cooking Continuous kraft cooking and oxygen delignification Continuous kraft cooking, oxygen delignification and QPZP bleaching Magnesium bisulfite cooking Batch kraft cooking Batch kraft cooking and oxygen delignification Batch kraft cooking, oxygen delignification and D(EOP)QPO bleaching

peeling and chemical analysis, all pulp samples were washed thoroughly with de-ionized water. Mechanical peeling and fractionation Material was obtained from the surface layer (peelings) and inner layer (peeled fibers) of the fibers by mechanical peeling and fractionation, as described previously (Sjo berg et al. 2002). This mechanical treatment removes outer secondary wall (S1) layer material, constituting approximately 1% of the total fiber weight, from the surface of the pulp fibers. The peeled fiber fraction, accounting for the remainder of the fiber weight, is composed primarily of inner secondary wall (S2 + S3) layers, but also contains portions of the S1 layer. Briefly, the pulp samples were first suspended in de-ionized water and primary fines were removed from the fibers by filtration. The resulting fiber fraction was re-suspended in de-ionized water at a consistency of 4.5%, subsequently subjected to gentle mechanical treatment in a disintegrator, and thereafter filtrated through a nylon cloth (pore size 100 m) to obtain peeled fibers and a filtrate containing surface layer material. This surface layer material was finally harvested from the filtrates by centrifugation and then lyophilized. The peeled pulp fibers, designated as inner layer material, were air-dried and analyzed.

Analysis of polysaccharide composition and contents of uronic acid residues The polysaccharide compositions and contents of uronic acids of the surface and inner layer materials were determined by enzymatic hydrolysis followed by capillary electrophoresis (CE), employing a method described in detail previously (Dahlman et al. 2000). The CE system utilized was a Beckman P/ACE MDQ capillary electrophoresis system (Beckman Coulter, Fullerton, CA, USA) equipped with a diode-array UV detector. Prior to the CE analysis, the sugars in the hydrolysates were derivatized with the UV chromophore 4aminobenzoic acid ethyl ester so that absorption at 306 nm could be used for quantitation. Extraction of the hemicelluloses In order to extract the hemicelluloses present, 100 mg of the sample was packed into a 1-ml syringe equipped with a glass wool plug at the needle end, after which approximately 1 ml of 17% aqueous sodium hydroxide was sucked into the syringe and extraction was allowed to proceed at room temperature for 3 h. Thereafter, the hemicellulose-containing extract was rapidly ejected from the syringe and an aliquot of this extract was diluted with the aqueous sodium hydroxide/acetate solution employed in connection with

328 size-exclusion chromatography (see below) to yield a final hemicellulose concentration of 0.21% (w/v). Subsequently, this solution was passed through a syringe filter with 0.45-m pores (Millipore, Bedford, Massachusetts) and then immediately injected onto the SEC column. The microscale procedure extracted virtually all of the hemicellulose from the pulps (1% or less hemicellulose remaining in the pulp after extraction). Size-exclusion chromatography Size-exclusion chromatography was performed with a system consisting of three columns containing Ultrahydrogel 120, 250 and 500 (Waters Associates) and linked in series to each other and to a refractometer that continuously measured the refractive index of the eluate (Waters). The mobile phase employed here was a 0.2 M sodium hydroxide/0.1 M sodium acetate solution (at pH 13). The hemicellulose mixture (100 l) was injected onto the SEC system and 0.13 l fractions, containing components with a narrow range of molar masses, were collected and subsequently analyzed by MALDI-MS, as described previously (Jacobs and Dahlman 2001a). The signal from the refractometer was processed on a standard PC utilizing the PL Caliber SEC software and interface (Polymer Laboratories Ltd., UK). Using this software, the molar mass parameters i.e., the numberaverage molar mass (Mn), weight-average molar mass (Mw) and polydispersity index (Mw/Mn) of the entire hemicellulose extract were calculated from the SEC profile, together with the MALDIMS analyses (see below). Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry The hemicellulose-containing fractions obtained by SEC were subsequently analyzed by MALDI-MS utilizing a HewlettPackard G2025 A MALDITOF mass spectrometer and MALDI probes coated with a Nafion polymer (Jacobs and Dahlman 2001a,b). In brief, each SEC fraction obtained as described above was pretreated with a cation-exchange resin (Amberlite IR-120, NH4+form) in order to remove the sodium ions present in the eluent and then concentrated by flushing with a gentle flow of nitrogen to approximately 20% of its original volume. One volume of this concentrated fraction was subsequently mixed with four volumes of the matrix solution (2% (w/v), 2,5-dihydroxybenzoic acid dissolved in 1:3 (v/v) methanol/water), after which 0.5 l of the solution thus obtained was deposited onto the tip of the MALDI probe, dried under vacuum and finally analyzed by MALDI-MS. Results Polysaccharide compositions and frequency of uronic acid side groups The mechanical peeling procedure employed here removed outer secondary wall (S1) layer materials, constituting approximately 1% of the total fiber weight, from the surface of the pulp fibers investigated. The peeled fiber fraction, accounting for the remainder of the fiber weight, was composed primarily of inner secondary wall (S2 + S3) layers, but also contained portions of the S1 layer. These findings agree well with our previous investigation on a number of softwood pulps produced by several different cooking and bleaching processes (Sjo berg et al. 2002). The surface (peelings) and inner (peeled fibers) layer materials obtained were characterized with respect to their polysaccharide composition and content of uronic acid residues employing a procedure developed earlier (Dahlman et al. 2000) in our laboratory and involving enzymatic hydrolysis and subsequent capillary electrophoresis. The major polysaccharide components of all of the materials from hardwood kraft pulps analyzed here (i.e., HK-U, HK-O and HK-TCF) were cellulose and xylan, with only small amounts of neutral glucomannan being detected, see Table 2. The surface layer materials from these hardwood kraft fibers exhibited 7075% higher contents of xylan (i.e., hexenuronoxylans) than did the corresponding inner layer materials. In contrast, both the surface and the inner layer materials from the sample of hardwood sulfite pulp (HS-U) contained much less xylan (i.e., 4-O-methylglucuronoxylans), and in this case the surface content was only 28% higher. Although the xylan contents of their surface layer materials were comparatively much greater,

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Table 2. Polysaccharide compositions and contents of uronic acid residues in the surface and inner layer materials obtained by mechanical peeling of hardwood and softwood chemical pulps. Samples Polysaccharides (mass %) Cellulose Hardwood pulps HK-U Surface layer Inner layer HK-O Surface layer Inner layer HK-TCF Surface layer Inner layer HS-U Surface layer Inner layer Softwood kraft pulps SK-U Surface layer Inner layer SK-O Surface layer Inner layer SK-ECF Surface layer Inner layer Glucomannan Xylan Uronic acids (mmol/kg) HexA MeGlcA

51.8 71.4 53.4 72.1 54.7 74.5 80.5 85.4

1.9 1.6 1.1 1.9 0.8 <0.5 3.5 2.1

46.3 27.0 45.6 26.0 44.4 25.5 16.0 12.5

87 74 87 76 19 34 <3 <3

16 19 20 19 18 19 5 5

74.3 80.5 76.8 81.7 81.1 83.6

9.3 8.7 7.8 7.3 6.2 6.7

16.4 10.8 15.4 10.9 12.7 10.6

40 30 38 32 <3 5

6 3 6 3 5 3

The determinations were performed by enzymatic hydrolysis and subsequent capillary electrophoresis. The results are mean values of two independent carbohydrate analyses on each sample. HexA hexenuronic acid and MeGlcA 4-O-methylglucuronic acid. (For an explanation of the sample designation, see Table 1.)

the quantities of uronic acid residues (i.e., HexA and MeGlcA) in surface and inner layer materials from both the unbleached and oxygen bleached hardwood kraft pulps (HK-U and HK-O) were rather similar. Thus, the frequency of HexA and MeGlcA side groups in the surface xylan polysaccharide chains of these pulps must be lower than that of xylan chains in the inner layer. Indeed, xylose:HexA:MeGlcA ratios of 100:2.8:0.5 and 100:4.1:1.0 were obtained for xylans in these surface and inner layer materials, respectively. The content of HexA residues in the hardwood kraft pulp was decreased significantly by the ozone treatment (sample HK-TCF, Table 1). However, the ozone charge employed in connection with bleaching in the present case was relatively limited (3 kg ptp), as a result of which approximately half of the HexA residues originally present were still detected in the pulp sample collected after the completion of bleaching. This finding was expected based on our earlier studies on the removal of HexA

residues from kraft pulps by ozone (BergnorGidnert et al. 1998). In contrast, the surface content of HexA residues was reduced by almost 80% as a consequence of ozone treatment, yielding fibers whose surface layers contained xylan polymers exhibiting a very low frequency of uronic acid side groups (i.e., a xylose:HexA:MeGlcA molar ratio of 100:0.6:0.5). As shown in Table 2, surface and inner layer materials obtained from the softwood pulps (samples SK-U, SK-O and SK-ECF) were also found to have somewhat different contents of cellulose, glucomannan and xylan. Once again, the largest relative quantities of xylans (i.e., arabinohexenuronoxylans) were present in the surface layer materials, but the differences in these cases were not as pronounced as for the hardwood fibers. In contrast to the xylan polymers, the softwood glucomannans were seen to be more-or-less uniformly distributed between the surface and inner layer materials analyzed.

330 The difference between the xylan contents of the surface and inner layer materials was most pronounced (50%) in the case of the unbleached softwood pulp (SK-U) and least (20%) for the completely ECF-bleached softwood pulp fibers (SK-ECF). This observation indicates that a portion of the softwood xylan, and especially from the surface layer, was dissolved into the process liquor under the conditions utilized for ECF bleaching, thus corroborating the substantial loss of xylans from the outer surface layer of softwood kraft fibers upon bleaching reported earlier by Luce (1964). In the case of the unbleached and oxygen delignified softwood kraft pulps (SK-U and SK-O), the carbohydrate compositions of the surface and inner layer xylans were somewhat dissimilar and indicated a lower frequency of side chain substituent sugar groups for the surface polymers (i.e., the xylose:HexA:MeGlcA:arabinose ratios were approximately 100:3.6:0.5:5.6 and 100:4.6:0.4:6.8, respectively). The quantities of HexA residues in the surface and inner layer materials from the fully ECF-bleached pulp were very low or even below the limit of quantification of the analytical procedure employed (i.e., <3 mmol/kg pulp). Molar mass parameters of the hemicelluloses The hemicelluloses present in the fiber layer materials obtained by mechanical peeling were subsequently extracted employing alkaline solutions and thereafter characterized with respect to their molar mass parameters. The microscale extraction procedure employed extracts almost all of the hemicelluloses in a relatively short time and hence minimizes any changes in the molar mass parameters of the hemicelluloses (Eremeeva and Bykova 1993; Jacobs and Dahlman 2001a). The molar mass analysis performed here involves the use of size-exclusion chromatography (SEC) to separate the hemicellulose mixtures into fractions containing components with a narrow range of sizes, followed by determination of the absolute molar masses of these fractions utilizing MALDIMS (Jacobs and Dahlman 2001a). The average molar mass parameters for the entire hemicellulose mixture are then calculated on the basis of the distribution curve obtained by SEC together with the MALDI-MS spectra. A major advantage of this approach is that mass spectrometry provides highly accurate absolute values for the molar mass parameters, hence eliminating the need for hemicellulose standard substances previously required to calibrate the curves obtained by SEC. Figure 1 depicts the molar mass distribution curves obtained from such analysis of the surface and inner layer xylans prepared from unbleached hardwood kraft and sulfite pulp fibers. As can be seen, the molar mass distribution curves for the xylans extracted from these two different kinds of pulps were quite dissimilar, with the sulfite 4-Omethylglucuronoxylans appearing at the lower end of the mass scale and the kraft hexenuronoxylans demonstrating considerably higher masses. Moreover, in the case of the hardwood kraft pulp, the surface xylans clearly exhibited higher molar masses than the xylans of the inner layer, i.e., these surface layer xylans must have longer chain lengths (a higher degree of polymerization). On the other hand, the distribution curves for the surface and inner layer xylans of the sulfite pulp show no such difference, indicating that these mixtures contain polymers with almost the same sizes. Table 3 gives the number average (Mn) and weight average (Mw) molar mass values, as well as the polydispersity index (Mw/Mn) values for the hemicelluloses present in the hardwood and softwood pulps investigated here. In the case of the unbleached hardwood kraft pulp (HK-U), the molar mass parameters Mw and Mn for the surface xylan polymers are approximately 30% higher than the corresponding values for the inner layer xylan. In contrast, in the case of the fully bleached sample (HK-TCF), the molar mass parameters of the surface xylan are only about 10% higher, indicating a somewhat more extensive depolymerization of surface xylans under the conditions employed for TCF bleaching. Figure 2 illustrates the molar mass distribution curves for the hemicellulose mixtures obtained by alkaline extraction of fiber layers originating from the unbleached softwood kraft pulp (SK-U). The distribution curve for the surface hemicellulose is clearly shifted towards higher masses relative to the curve for the inner layer hemicellulose, thus also in this case indicating the presence of longer polymers at the surface of kraft pulp fibers. The materials from the fibers in the unbleached and fully ECFbleached softwood pulps exhibited relatively similar mass parameters (Table 3), i.e., the ECF

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Figure 1. Molar mass distribution curves obtained by SEC/MALDI-MS analysis of the hemicellulose mixtures prepared by alkaline extraction of the surface and inner layer materials from unbleached hardwood kraft pulp (HK-U) and unbleached hardwood sulfite pulp (HS-U). The analyses were performed with a SEC system consisting of three columns, Ultrahydrogel 120, 250 and 500, linked in series to each other and to a refractometer. The aqueous mobile phase employed was a 0.2 M sodium hydroxide and 0.1 M sodium acetate solution.

Figure 2. Molar mass distribution curves obtained by SEC/MALDI-MS analysis of the hemicellulose mixtures prepared by alkaline extraction of the surface and inner layer materials from unbleached softwood kraft pulp (SK-U). The analyses were performed with a SEC system consisting of three columns, Ultrahydrogel 120, 250 and 500, linked in series to each other and to a refractometer. The aqueous mobile phase employed was a 0.2 M sodium hydroxide/0.1 M sodium acetate solution.

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Table 3. Molar mass parameters of the hemicelluloses extracted by 17% aqueous sodium hydroxide from the surface and inner layer material of hardwood and softwood chemical pulps. The analyses were performed using size-exclusion chromatography in combination with off-line MALDI mass spectrometry. The results are mean values of two analyses. (For an explanation of the sample designation, see Table 1.) Hemicellulose sample Mass parameter Mw Hardwood pulps HK-U Surface layer Inner layer HK-O Surface layer Inner layer HK-TCF Surface layer Inner layer HS-U Surface layer Inner layer Softwood kraft pulps SK-U Surface layer Inner layer SK-O Surface layer Inner layer SK-ECF Surface layer Inner layer Mn Mw/Mn

19 600 15 000 17 200 13 900 14 400 13 100 6600 6900

15 900 12 100 12 800 11 100 11 200 9 900 5600 5900

1.2 1.2 1.3 1.2 1.3 1.3 1.2 1.2

20 700 15 800 23 000 17 200 20 200 15 500

14 700 11 600 17 600 12 600 16 100 11 900

1.4 1.4 1.3 1.4 1.3 1.3

bleaching conditions had no apparent effect on these parameters in this case. Discussion The fibers present in all of the hardwood kraft pulps investigated here demonstrated a much higher relative content of hexenuronoxylan in their surface layer than in their inner layer material. It is noteworthy that the relative contents of xylan in these fiber surfaces are also significantly higher than the value previously reported by Meier (1961) for the relative xylan content of the outer secondary cell wall layer of native hardwood (birch) fibers. Moreover, the xylan polymers present in the surface layers of the hardwood kraft fibers exhibited a relatively low frequency of uronic acid side groups. It has been noted earlier that hardwood xylans

containing relatively few uronic acid side groups are sparingly soluble in aqueous alkaline solutions (Wikstro m 1968) and exhibit a pronounced tendency to adsorb to the surface of cellulose (Hansson and Hardler 1969; Hansson 1970). It is well known that linear polysaccharide chains of more-or-less uniform structure can fit together for strong intermolecular binding and can form ordered arrays that tie molecular segments together in effective cross-links (Whistler 1973). When brought in solution, such polysaccharide chains can easily segmentally recombine and form aggregates that finally precipitate or adsorb onto cellulose surfaces. Therefore, it is reasonable to propose that during the kraft cooking process, xylans with a low frequency of uronic acid side groups are preferentially deposited onto the surface layers of the hardwood pulp fibers characterized here. Indeed, the observation that the xylans in the surface layer of unbleached hardwood kraft fibers demonstrated approximately 30% higher average molar mass values and much lower frequency of uronic acids than do inner layer xylans, lends additional support to the suggestion that large essentially linear xylan polymers exhibiting low solubility are preferentially re-adsorbed onto fiber surfaces. Altogether, these findings indicate that xylan readsorption occurs under the conditions used for kraft cooking, coating the surface of the hardwood fibers with large hexenuronoxylan polymers exhibiting a low frequency of uronic acid side groups. This conclusion is in good agreement with several earlier studies suggesting that some of the xylan polymers dissolved into kraft cooking liquor are subsequently re-adsorbed onto the fibers (Yllner and Enstro m 1957; Aurell 1965; Imai et al. 1997). Furthermore, in a recent investigation we observed that hexenuronoxylans present in black liquors resulting from hardwood kraft cooking can also be adsorbed onto the surface of softwood fibers during kraft cooking in a pulp mill (Sjo berg et al. 2001). In addition, our present analyses demonstrate that ozone treatment exerts a more pronounced effect on the content of HexA residues in the surface layer of hardwood pulp fibers than on the corresponding content of the inner fiber layer. As much as 80% of the HexA residues originally present in the surface material were found to be removed by bleaching, clearly indicating a decrease in the extent of reaction with ozone at greater

333 depths in the fibers. Indeed, it has been shown previously that ozone reacts rapidly with lignin residues located in the outer layer of fiber wall, while reaction with such residues in the inner layer appears to be limited by the penetration of ozone into the fiber (Wang et al. 1997). Obviously, this reaction phenomenon could also explain the more effective reaction of ozone with the surface HexA residues observed here. Furthermore, the molar mass parameters obtained for the xylans from TCF-bleached hardwood pulp revealed that the surface polymers are depolymerized to a greater extent under ozone bleaching conditions. The fibers in softwood kraft pulps also demonstrated relatively higher contents of xylans in their surface layers. This observation agrees well with our earlier study on different types of chemical pulps obtained from the same batch of softwood chips by various cooking procedures (Sjo berg et al. 2002). In contrast, native softwood fibers demonstrate a more even distribution of xylans across the fiber cell wall (Meier 1961; Hardell and Westermark 1981). Hence, once again our findings are indicating selective enrichment of xylan in the surface layer during the process of kraft cooking. The arabino(hexenurono)xylans in the softwood fibers examined here exhibited a tendency to be solubilized by the bleaching conditions employed. In addition to the uronic acid residues present in hard- and softwood xylans, softwood xylans also contain substantial numbers of arabinose residues as substituents on the backbone. Such arabinose residues influence the solution properties of arabinoxylans (Dea and Rees 1973; Whistler 1973; Andrewartha et al. 1979). Hence, the frequency of arabinose side groups in the softwood xylans may in part explain their somewhat greater tendency to be solubilized. The solubilization of softwood kraft xylan under conditions employed for ECF bleaching was found here to be most pronounced for the surface layer of the fiber. In contrast, analysis of the molar mass parameters indicated that the backbone of softwood xylan remains essentially intact under these same conditions. Therefore, since all of the hexenuronic acid residues were removed by the treatment with chlorine dioxide, the xylans remaining on the surface of the softwood fibers after completion of the ECF bleaching process are predominantly uncharged long linear polymers. Conclusions The characterizations performed here have demonstrated that the surfaces of the fibers present in hardwood and softwood kraft pulps are coated to a certain extent by relatively long xylan polymers with a low frequency of uronic acid side groups. In the case of the hardwood fibers, the surface layer contains much higher relative levels of xylan polymers with high molar masses and low uronic acid frequency than do the inner layers. A similar situation was observed for the softwood kraft pulp fibers. The xylan at the surface of hardwood kraft fibers is resistant towards solubilization under the TCF bleaching conditions examined here. In contrast, the hexenuronic acid residues on the fiber surface were found to be removed to a greater extent than in the case of the inner layer, indicating the existence of a gradient for reaction with ozone across the fiber cell wall. The xylan polymer remaining on the surface of the softwood fibers after completion of the ECF bleaching process is predominantly long and uncharged (very low frequency of uronic acids). In summary, the present investigation clearly demonstrates that the effects of cooking and bleaching on the molecular properties of hemicelluloses present in pulp fibers are most pronounced for the surface layer. Consequently, information concerning the quantity and properties of the hemicelluloses located in the surface layer may therefore serve as a sensitive indicator for predicting the potential surface properties and bonding ability of different kinds of chemical pulp fibers. Acknowledgments Research funding from the Jacob Wallenberg Research Foundation (to A.J.) and from the Swedish Council for Forestry (to J.S.) is gratefully acknowledged.

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