Topochemistry of physical and chemical pretreatments of biomass as investigated by FE-SEM, XPS and ToF-SIMS

Surface chemistry is of great importance in plant biomass engineering and applications. The surface chemical composition of biomass which includes lignin, carbohydrates and extractives influences its interactions with chemical agents, such as pulp processing/papermaking chemicals, or enzymes for different purposes. In this thesis, the changes in the surface chemical composition of lignocellulosic biomass after physical modification for the improvement of resulting paper properties and chemical treatment for the enhancement of enzymatic hydrolysis were investigated. Low consistency (LC) refining was used as physical treatment of bleached softwood and hardwood pulp samples, and the surface chemistry of refined samples was investigated. The refined pulp was analysed as whole pulp while the fines-free fibre samples were characterized separately. The fines produced in LCrefining contributed to an enlarged surface specific area as well as the change of surface coverage by lignin and extractives, as investigated by X-ray photoelectron spectroscopy (XPS). The surface coverage by lignin of the whole pulp decreased after refining while the surface coverage by extractives increased both for pine and eucalyptus. In the case of pine, the removal of fines resulted in reduction of the surface coverage by extractives, while the surface coverage by lignin increased on fibre sample (without fines). In the case of eucalyptus, the surface coverage by lignin of fibre samples decreased after the removal of fines. In addition, the surface distribution of carbohydrates, lignin and extractives of pine and eucalyptus samples was determined by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). LC-refining increased the amounts of pentose, hexose and extractives on the surface of pine samples. ToF-SIMS also gave clear evidence about xylan deposition and reduction of surface lignin distribution on the fibre of eucalyptus. However, the changes in the surface chemical composition during the physical treatment has led to an increase in the adsorption of fluorescent whitening agents (FWAs) on fibres due to a combination of electro-static forces, specific surface area of fibres and hydrophobic interactions. Various physicochemical pretreatments were conducted on wood and non-wood biomass for enhancing enzymatic hydrolysis of polysaccharides, and the surface chemistry of the pretreated and enzymatically hydrolysed samples was investigated by field emission scanning electron microscopy (FE-SEM), XPS and ToF-SIMS. A hydrotrope was used as a relatively novel pretreatment technology both in the case of wood and non-wood biomass. For comparison, ionic liquid and hydrothermal pretreatments were applied on softwood and hardwood as well. Thus, XPS analysis showed that the surface lignin was more efficiently removed by hydrotropic pretreatment compared to ionic liquid or hydrothermal pretreatments. SEM analysis also found that already at room temperature the ionic liquid pretreatments were more effective in swelling the fibres compared with hydrotropic pretreatment at elevated temperatures. The enzymatic hydrolysis yield of hardwood was enhanced due to the decrease in surface coverage of lignin, which was induced by hydrotropic treatment. However, hydrotropic pretreatment was not appropriate for softwood because of the predominance of guaiacyl lignin structure in this material. In addition, the reduction of surface lignin and xylan during pretreatment and subsequent increase in cellulose hydrolysis by enzyme could be observed from ToF-SIMS results. The characterisation of the non-wood biomass (e.g. sugarcane bagasse and common reed) treated by hydrotropic method, alkaline and alkaline hydrogen peroxide pretreatments were carried out by XPS and ToF-SIMS. According to the results, the action for the removal of the surface lignin of non-wood biomass by hydrotropic pretreatment was more significant compared to alkaline and alkaline hydrogen peroxide pretreatments, although a higher total amount of lignin could be removed by alkaline and alkaline hydrogen peroxide pretreatment. Furthermore, xylan could be remarkably more efficiently removed by hydrotropic method. Therefore, the glucan yield achieved from hydrotropic treated sample was higher than that from samples treated with alkaline or alkaline hydrogen peroxide. Through the use of ToF-SIMS, the distribution and localization of lignin and carbohydrates on the surface of ignocelluloses during pretreatment and enzymatic hydrolysis could be detected, and xylan degradation during enzymatic hydrolysis could also be assessed. Thus, based on the results from XPS and ToF-SIMS, the mechanism of the hydrotropic pretreatment in improving the accessibility of enzymes to fibre and further ameliorating of the enzymatic saccharification could be better elucidated.

Breviarium Fratrum Praedicatorum (MS C.IV.10)

Two probably originally distinct but roughly contemporary books (I-II, copied by three scribes, A-C): A psalter and a Dominican breviary. Complete critical and codicological description of the book and its contents available in the Codices Fennici -database.

Contents: I: Psalter: Fols. 7r–76va, Psalter, with additional hymns, concluding with Te Deum; Fols. 76vb–77vb, the Athanasian Creed; Fols. 77vb–80v, litany and other prayers. II: Dominican breviary: Fols. 1r–6v, English Dominican calendar (Jan.–Dec.); Fols. 81r–242v, 276r–312r, proprium de tempore (defect), from the First Advent to the First Sunday after Trinity, and from septuagesima in mensis Augusti to the 25th Sunday after Trinity; Fols. 313ra–318v, Office for the dedication of a church; Fols. 243r–275v, 319r–334v, 353r–v, 335r–352v, 354r–371r, proprium de sanctis (defect), from the beginning up to the office of Mary Magdalene, with a misplaced leaf, fol. 353, at translatio B. Dominici, and, after several missing gatherings, the end of commune sanctorum; Fol. 371v, originally empty, with office for St Ursula added in a saec. XIV hand.

Codex Westh (MS C.III.19, kirkollinen käsinkirjoitettu kokoomanide)

Koodeksiin sisältyy kolme tekstikokonaisuutta. Ydinosan muodostavat suomalainen kirkkokäsikirja ja messu eli jumalanpalvelusjärjestys, joilla on oma, alkuperäinen sivunumerointinsa. Kolmas kokonaisuus on suomennos saksalaisen Urbanus Rhegiuksen laatimasta sielunhoidon opaskirjasta Sieluin vahvistus, lohutos ja lääkitys.

Graduale (MS C.III.36, "Ilmajoen Graduale II")

A very small gradual and hymnary, for the most part copied in the last years of the sixteenth century or in the first quarter of the seventeenth. Assuming that Henricus Jacobi indeed signed his name in the sixteenth century (as Kurvinen reports), some of the manuscript was copied in that century: in lieu of a more accurate indicator the date of the manuscript appears to fall between 1589 and Mathias Benedicti's additions in 1635. The book was kept, perhaps even copied but certainly used, at Ilmajoki from the seventeenth century, and came from there to the University Library.

Antiphonarium (MS A.ö.II.29, Ilmajoen antifonarium)

Complete critical and codicological description of the book and its contents available in the Codices Fennici -database.

Psalterium Davidicum (MS C.IV.24)

Complete critical and codicological description of the book and its contents available in the Codices Fennici -database.

Graduale (MS A.ö.II.55, Ilmajoen graduale)

A graduale (defect) from Ilmajoki. Written in three parts, part I (fols. 1-134) dating probably from the 1540's, part II (fols. 135-140) probably from the 1550's and part III (fols. 141-194) from the 1530's.

Graduale (MS Coll. 762.3)

A Lutheran gradual copied apparently by one scribe at the end of the sixteenth century and probably repaired (fol. 29) in the beginning of the seventeenth century.

Graduale (MS C.ö.III.17)

A Lutheran gradual from Kalanti. As covers used a fragment of the Liturgical calendar of the Diocese of Turku, Saec. XIV 2/2, Diocese of Turku.

Legendarium (MS C.ö.I.1)

Much of the manuscript is taken up by a collection Sunday sermons and by a selection from Legenda Aurea. The manuscript features several scribes and may be a result of compiling text from different sources.

Summa Theologiae (MS Coll. 762.2)

An abridgement or selections from Thomas Aquinas, Summa theologiae. The text strongly modifies and abridges the original.

Sermones de tempore et de sanctis (MS C.ö.I.6)

Complete critical and codicological description of the book and its contents available in the Codices Fennici -database.

Missale (MS C.ö.IV.7, "Oripään missale I")

Complete critical and codicological description of the book and its contents available in the Codices Fennici -database.

Kyriale, Sequentiarium (MS C.ö.I.23)

A graduale and a sequentiarium were copied in the reformation period for use in the Diocese of Turku, possibly in Raisio. The graduale in Finnish appears to depend on Jacobus Finno's hymnbook of 1586, whereas the sequentiarium is probably somewhat older, possibly even coeval with Mathias Westh's liturgical codex (1540's). The present fragments probably come from at least two (possibly three) originally distinct books or booklets.

Antiphonarium (MS C.ö.III.22, "Pöytyän antifonarium")

A Lutheran copy of a Dominican antiphonary, copied with modifications some time after the middle of the sixteenth century. The very selective sanctoral reflects Lutheran tastes, with only biblical saints (and possibly St Henry).