The cell wall of plant fibers may contain irregular regions called dislocations. This study evaluated the effect of chemical pretreatment as a mechanochemical dislocation initiator in unbleached and bleached Eucalyptus sp. fibers. Accordingly, bleached and unbleached pulps of eucalyptus were subjected to chemical pretreatments with sodium hydroxide at concentrations of 5% for 2 h, 10% for 1 h and 10% for 2 h or with hydrogen peroxide. The extent of dislocations was evaluated by polarized light microscopy. Based on the observation, an index of dislocations (ID) expressing their ratio of cell wall as per two-dimensional (2D) imaging and their angle relative to the longitudinal direction of the fiber were estimated. Chemical pretreatments increased the ID for bleached and unbleached fibers as well as increased the changes in the curl of bleached and unbleached fibers for chemical pretreatments. Chemical pretreatment extracted the hemicellulose of the fiber cell wall causing some fiber to curl, which in turn generated new dislocations and modifications in the dislocation angles which may be useful for improving the deconstruction process of the cellulose fibers.

The current environmental legislations recommend monitoring chemical contaminants such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans before the use of sewage sludge on the agricultural land. In this study, a solid-liquid extraction with low-temperature purification (SLE-LTP) was optimized and validated to determine 2,3,7,8-tetrachlorodibenzo-p-dioxin and 2,3,7,8-tetrachlorodibenzofuran in sewage sludge and soil samples. The analyses were performed by gas chromatography-mass spectrometry operating in the selective ion mode (GC-MS-SIM). Acetonitrile:ethyl acetate 6.5:1.5 (v/v) was the best extraction phase, and the recoveries percentages were close to 100%. The linearity was demonstrated in the range of 1.25-25 µg L of 1.25-20 µg L for sewage sludge and soil, respectively. Matrix effect was proved for the two compounds and in the two matrices studied. Extraction percentages were between 78 and 109% and relative standard deviations ≤ 19%. The proposed method is faster than methods described in the literature because showed a few steps. The quantification limits (LOQ) in sewage sludge were 6.4 and 32 ng TEQ kg for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. In soil, LOQs were 0.8 and 8.0 ng TEQ kg for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. These values are lower than the maximum residue limits established by European Legislation. The method was applied to 22 agricultural soil samples from different Brazilian cities and 2,3,7,8-TCDF was detected in one of these samples.

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This study aimed to assess the effect of drying unbleached Eucalyptus cellulose fibers after the application of pretreatments in order to optimize the microfibrillation process, as well as to evaluate the efficiency of NaOH pretreatments in reducing energy consumption for production of microfibrillated cellulose (MFC). Pretreatments with 0 wt% (untreated), 5 wt% and 10 wt% NaOH were evaluated. The length and width of the fibers pretreated with NaOH decreased significantly, mainly with hasher pretreatments.The removal of hemicellulose from the fiber cell wall was an important factor concerning the degree of fibrillation of the fibers. Pretreating fibers with 5 wt% NaOH for 2 h increased the water retention value (WRV), in addition to presenting the lowest energy consumption for fibrillation, promoting energy savings of up to 48%. Pulps that were not dried after the NaOH pretreatments incurred in easier microfibrillation and lower energy consumption when comparing to the dried pulp, which shows the negative impact of drying on the fibers to obtain the MFC.

No abstract

Sugars are a sustainable platform for producing chemicals and polymers, while cellulose nanofibers (CNF) are sustainable materials with high specific mechanical properties that have an important role to play in many applications. This study highlights the feasibility of producing sugars and CNF using high dry matter (DM) content of 20 %. A commercial enzyme cocktail at low dosage, 5 mg EP/g DM, and a high 15 mg EP/g DM, were used to hydrolyze the pulp cellulose to produce sugars and CNF. HPLC was used to evaluate the cellulose conversion rate and amount of sugar realized. The CNF were studied using TEM, the diameter of the CNF were measured and estimate the crystallinity. The cellulose conversion plateaued at about 48 h for both the low and high dosage, indicating inhibition due to higher sugar concentration and/or increased recalcitrance of the remaining CNF. The CNF obtained at low enzyme indicated the fibrils were insufficiently separated. At the high dosage, less clumps were observed and with smaller diameter than with the low enzyme dosage. The high dosage also produced CNF with significantly higher crystallinity index, confirming that amorphous cellulose portions readily underwent enzymatic hydrolysis and left more recalcitrant CNF.

No abstract

The objective of the present work was to evaluate the use of Raman microspectroscopy analysis to assess changes in cellulose micro/nanofibril structure from fibers subjected to different pre-treatments. Pulp fibers were pre-treated with 5 wt% NaOH for 2 h, 10 wt% NaOH for 1 h, and endoglucanase-type enzymes to improve nanofibrilation. After the pre-treatments, the fibers were mechanically fibrillated to produce cellulose micro/nanofibrils, which were made into films to be analyzed. Fibers pre-treated with 5 wt% NaOH produced 59% micro/nanofibrils with average diameter less than 30 nm, for Eucalyptus, and 46% of micro/nanofibrils, with the same diameter, for Pinus. However, the enzymatic pre-treatment was the most efficient, resulting in 83% of micro/nanofibrils for Eucalyptus and 78% for Pinus. This corroborates with the lowest values of the 1.096/2.896 ratio and degree of polymerization, indicating chain shortening in cellulose. X-ray diffraction and Raman microspectroscopy crystallinity results presented similar tendencies, with increased crystallinity caused by all pre-treatments, being 5 wt% NaOH for 2 h the highest, with 70%, for Eucalyptus and Pinus. Enzymatic pre-treatment has produced the best fibrillation and greater crystallinity. The present work has shown a reliable way of assessing cellulose structure using Raman microspectroscopy.