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Lignin, a natural pol2ymer with a complex structure that is difficult to separate, is prone to C-C bond condensation during the separation process. To reduce the condensation of lignin, here, a novel method is proposed for separating the components by using a combination of maleic acid (MA)/ozone (O 3 ) to co-treat wheat straw. The removal of lignin, glucan, and xylan was 38.07 ± 0.2%, 31.44 ± 0.1%, and 71.98 ± 0.1%, respectively, under the conditions of ball-milling of wheat straw for 6 h, reaction temperature of 60 °C, and O 3 holding time of 9 min. Lignin-rich solutions were collected to extract the dissolved lignin (DL) after washing the treated samples. The DL obtained under MA/O 3 conditions had a carboxyl group (-COOH) content of 2.96 mmol/g. The carboxyl group of MA underwent esterification with the hydroxyl group (-OH) at the γ position of lignin and O 3 reacted on the positions of the lignin side chain or the phenolic ring, resulting in a break in the side chain and the opening of the phenolic ring to introduce the carboxyl group. The 2D-HSQC-NMR results revealed that the phenolic ring-opening reaction of lignin in the presence of O 3 was essentially free of β-β and β-5 condensation bonds.

This work focuses on the influence of ozone pretreatment on the fractionation and solubilization of sugarcane bagasse and soda bagasse pulp fibers in sodium hydroxide/urea solution, as well as the application of regenerated cellulose for producing edible films. The methodology involved pretreating lignocelluloses with ozone for 20 to 120 min before dissolving in sodium hydroxide/urea solution. The influence of the pretreatment conditions on cellulose dissolution yield was investigated. Regenerated cellulose films were then formed, with and without the addition of 2 % chitosan. Mechanical, physical, structural, thermal, and antimicrobial attributes were determined as a function of ozonation conditions of raw materials and chitosan content. The findings exhibited positive effects of short ozonation on enhancing mechanical strength, cohesion, and hydrophobicity. The prolonged ozonation of 120 min demonstrated optimal improvements in continuity, swelling, and antibacterial resistance of obtained films. Incorporating chitosan enhanced tensile performance, stiffness, and vapor barriers but increased moisture absorption. Tailoring the activation of biomass through ozone pretreatment and chitosan addition resulted in renewable films with adjustable properties to meet diverse packaging requirements, particularly for fruit protective coatings, ensuring the preservation of post-harvest quality., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

This study adopted the combination of activated sludge treatment and catalytic ozonation technology to efficiently remove the high concentration of ammonia nitrogen from landfill leachate. Through optimizing the parameters continuously, the COD, NH 4 + -N, UV 254 and colority respectively descended to 417.75 ± 6.72 mg/L, 9.77 mg/L, 1.98 ± 0.04 and 40 times, and 3D fluorescence also reduced significantly within 14 days. Target genes of AOB-amoA, nxrA, napA, nirS and nosZ analysis indicated that ammonia-oxidizing bacteria, nitrated bacteria, and denitrifying bacteria played a key role on nitrogen removal, aerobic denitrifying bacteria was dominated especially. The nitrogen removal process was as follows: catalytic ozonation converted nitrogen-containing organic matter into NH 4 + -N, then NH 4 + -N was converted into NO 2 - -N and NO 3 - -N with the action of ammonia oxidation, nitrification and catalytic ozonation. Finally, the denitrification microorganisms transformed NO 3 - -N or NO 2 - -N to N 2 . Therefore, this coupled process realized the nitrogen removal effectively from landfill leachate., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Ultraviolet/ozone (UV/O 3 ) treatment has been reported to be an effective method to modify properties such as wettability, adhesion or adsorption of plastic surfaces. The change in the surface is measured by contact angle analysis, which employs liquids and their surface tensions (ST) to estimate the surface energy (SE). We found two different practices in the scientific community: (1) the majority of researchers adopted the ST value of liquids from the literature, while (2) other researchers conducted real-time measurements in the lab under ambient conditions prior to SE estimation. To the best of our knowledge, there is no study that compares the difference between the two practices. One study was found to show different SE methods generating unequal SE values for the same substrate. However, there was no definitive conclusion backed by general thermodynamics rules. In this study, we presented (1) a statistical significance test that showed the literature and experimental ST values are significantly different, and studied (2) the effect of different liquid pairs on the SE estimation for UV/O 3 treated poly(ethylene terephthalate) (PET) substrate. Modification techniques such as atmospheric pressure plasma or chemical modification were studied previously to examine PET's wettability and the SE. The UV/O 3 treatment was studied to improve adhesion and to modify its chemical properties for adsorption. In contrast, we studied (3) the effect of UV/O 3 on wettability at different timeframes and addressed (4) how to control unequal SE based on a method that was refined on a rigorous thermodynamic three-phase system. It must be noted that this method can be generalized to other types of solid surfaces to estimate thermodynamically self-consistent SE values. This work also provides (5) a web-based calculator that complements computational findings available to the readership in the data availability section., (© 2022. The Author(s).)

The lignin pyrolysis products generated by biomass combustion make an essential contribution to the formation of secondary organic aerosols (SOAs). The ozone-initiated oxidation of guaiacol, syringol and creosol, major constituents of biomass burning, were investigated theoretically by using the density functional theory (DFT) method at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. Six primary addition reaction pathways and further decomposition routes with corresponding thermodynamic values were proposed. The Criegee intermediates can be excited by small molecules, such as NO x , H 2 O in the atmosphere, and would further proceed via self-decomposition or isomerization. The most predominant product for ozonation of guaiacol is the monomethyl muconate (P1). At 295 K and atmospheric pressure, the rate constant is 1.10 × 10 -19 cm 3 molecule -1 s -1 , which is lies a factor of 4 smaller than the previous experimental study. The branching ratios of the six channels are calculated based on corresponding rate coefficient. The present work mainly provides a more comprehensive and detailed theoretical research on the ozonation of methoxyphenol, which aspires to offer novel insights and reference for future experimental and theoretical work and control techniques of SOAs caused by lignin pyrolysis products.

The pulp and paper industry is highly dependent on forest and water resources. It has more concerns on fair utilization of these resources and their conservation for its further expansion. Present study emphasizes on the use of rice straw (agro waste) in papermaking to protect wood based resources. It further deals with ozone bleaching (Z) prior to elemental chlorine free bleaching that proved to be significant in terms of reducing the effluent load specially the reduction in toxic, recalcitrant and carcinogenic compounds. Z based sequences resulted in pulp brightness of ∼85% that was 3.6% higher than the elemental chlorine free bleaching. Bleached pulps of Z based sequences were found to be having better strength properties than elemental chlorine based sequence and thus may be adopted as improved bleaching technology. The analysis of handsheets prepared after pulp bleaching was performed using X-Ray diffraction, ATR-FTIR and SEM. Incorporating ozone stage resulted in marked reduction of 58% and 63% in total solids in bleaching wastewater. Reduction of more than 80% in BOD, COD and adsorbable organic halides was achieved in Z based bleaching in comparison to chlorine bleaching. The amount of chlorophenols, guaiacols, catechols, vanillins and syringols became negligible (approx. 90% reduction) in effluents of Z based bleaching sequences. The chlorine dioxide followed by peroxide bleaching after Z stage was found to be the most promising to reduce the effluent load., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Herein a Mn-deposited sepiolite catalyst was obtained through a facile co-precipitation method, and then used as the heterogeneous ozonation catalysts applied to the tertiary treatment of regenerated-papermaking wastewater. During the process, the as-prepared catalyst was endowed with higher Brunauer-Emmett-Teller specific surface area of 412.3 m 2 /g compared to 124.6 m 2 /g of the natural sepiolite. Hence, in the adsorption of methylene blue, the as-prepared catalyst was observed with a very high removal rate of 96.2% although a little lower than the modified sepiolite of 97.5% in 100 min. And for practical application, the catalyst was used for treating the effluent from regenerated-papermaking industry, via a heterogeneous catalytic ozonation process. Consequently, the highest color removal rate of 99.5%, and the highest chemical oxygen demand (COD) removal efficiency of 73.4% were achieved in 20 and 30 min, respectively. As a result, the treated wastewater was more biodegradable and less toxic; the biochemical oxygen demand (BOD 5 )/COD value could reach 0.41. Moreover, the catalyst showed superior stability at successive ozonation runs. The main possible reaction pathway is also presented. The results indicate that catalytic ozonation was proved to be effective when Mn/sepiolite was used as catalysts applied to the advanced treatment of regenerated-papermaking wastewater.

The formation of carbonyl groups during the ozone treatment (Z) of eucalyptus (Eucalyptus grandis and Eucalyptus urophylla hybrid) kraft pulps and their behaviors during subsequent alkaline stages were investigated by the CCOA method with carbazole-9-carboxylic acid [2-(2-aminooxethoxy)-ethoxy] amide (CCOA) as the carbonyl-selective fluorescence label. Several pulp samples with or without lignin and hexenuronic acids (hexA) were used to elucidate the effects of these components when present in unbleached kraft pulp. Both hexA and lignin increased the formation of carbonyl groups on cellulose and hemicellulose during ozonation. It was concluded that radicals are likely formed when ozone reacts with either lignin or hexA. These carbonyl groups were involved in cellulose depolymerization during subsequent alkaline extraction stages with sodium hydroxide (E) and alkaline hydrogen peroxide (P, in ZEP or ZP). Their numbers decreased after E but increased during P when H2O2 was not stabilized enough. Several ways to minimize the occurrence of carbonyl group formation are suggested., (Copyright © 2014. Published by Elsevier Ltd.)

Cork boiling wastewater pollutants were fractionated by sequential use of four ultrafiltration membranes and five fractions were obtained: four retentates (>100, 50-100, 20-50 and 10-20 kDa) and one permeate (<10 kDa); which were used to study the correlation of molecular size with biodegradability and toxicity before and after ozonation. The results show that molecular size is correlated with organic load and restrains biodegradability. The fraction with >100 kDa corresponds to 56% of the organic load and the one with <10 kDa only 8%. The biodegradability of fractions increased 182% with fractions molecular size reduction from >100 to <10 kDa and the chemical oxygen demand (COD) was from 3436 to 386 mg L(-1). For biodegradability enhancement the best outcome of ozonation was obtained with compounds having molecular size >20 kDa and range from 5% up to 175% for applied ozone doses to COD ratios between 0.15 and 0.38., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Biodegradability enhancement and detoxification of cork boiling wastewater (CBW) are required for the successful implementation of biological treatment options. We studied the possibility of achieving these goals through ozonation pre-treatment by experimenting on the effect of ozone dose and pH. The CBW used had a pH of 5.81, a chemical oxygen demand (COD) of 1,865 mg L(-1), a biochemical oxygen demand (BOD5) of 498 mg L(-1) and total phenol (TP) and tannin compounds concentrations of 523 and 399 mg L(-1), respectively. The ozone doses ranged from 0.27 to 2.63 for the O3(applied)/COD0 ratios with samples at natural pH and set to 3.33 and 9.96. Ozonation allowed the BOD20/COD ratio (biodegradability index) to increase from 0.37 to 0.63 and a toxicity reduction from 3.08 to 1.24 TU (Microtox). The corresponding removals obtained were 15.2-62.0%, 38.4-83.2% and 56.7-92.1% for COD, TP and colour, respectively. The best outcome of ozonation pre-treatment requires O3(applied)/COD0 ratios over 1.5 and an acid pH. The increase of TP removals with ozone dose at acid pH led to biodegradability enhancement and CBW detoxification. However, for similar conditions the highest COD removals were obtained at alkaline pH due to the hydroxyl radicals' high oxidation ability but lack of selectivity.

To study the fast kinetic decolourisation of textile dyes by ozone a continuous quench-flow system was used. This system has not been used before for these purposes. Reaction times in the range of 7-3000 ms were explored. The reaction was quenched with potassium iodide, which proved to be very effective, and the indigo method was used to follow the ozone concentration. Dyes from the most representative chemical classes currently used in the textile industry, i.e. azo and anthraquinone, were selected. Using the initial slope method, the effect of dye and ozone concentrations was researched and the kinetic equations thus established. Using tert-butyl alcohol, as radical scavenger, and pH close to 2.5, the second-order rate constant of the reactant dyes at 280 K varies in the range of 1.20x10(4)-7.09x10(5)M(-1)s(-1); the Acid Orange 7 exhibiting thus its lowest value, the Acid Blue 45 its highest value and the Acid Green 25 and 27 and Direct Yellow 4 intermediate values (approximately 1.6x10(5)M(-1)s(-1)). Without radical scavenger and the pH close to 4, the reaction rate increases one order of magnitude, but, on the reverse, the efficiency of ozone to decolourisation decreases., (Copyright 2010 Elsevier B.V. All rights reserved.)

Ozone-enhanced catalytic oxidation of methanol has been conducted at mild temperatures of 100-250 degrees C using a V2O5/ TiO2 catalyst prepared by the sol-gel method. The catalyst was characterized using XRD, surface area measurements, and temperature-programmed desorption of methanol. The oxidation of methanol with ozone in the absence of a catalyst gave about 30% conversion at 100 degrees C. Methanol oxidation over a V2O5/TiO2 catalyst at 100 degrees C gave very little conversion with oxygen, whereas the conversion increased to 80% with ozone. Methanol, having an inlet stream concentration of 15 000 ppmv, can be completely oxidized to CO(x) with an ozone-to-methanol ratio of 1.2, a temperature of 150 degrees C, and a gas hourly space velocity (GHSV) of 60 000 h(-1). The apparent activation energy with ozone was calculated to be ca. 40 kJ/mol, which is much lower than that calculated with oxygen (60 kJ/mol). At low methanol conversion methyl formate was the main product, whereas higher conversions favored oxidation to CO(x). The results imply a consecutive reaction of adsorbed methanol species, favoring selectivity toward methyl formate at lower temperatures and ozone-to-methanol ratios and CO(x) at higher temperatures and ozone-to-methanol ratios. Langmuir-Hinshelwood kinetics was used to model the reaction with and without ozone in the feed. The model parameters were obtained using least-squares fit to a selected set of experimental data, and the model was subsequently compared to all experimental data obtained in this study.

Studies were conducted on the response of 2,4,6-trichlorophenol (1), 2,3,4,5-tetrachloro-phenol (2) and 4,5-dichloroguaiacol (3) toward advanced oxidation processes, such as UV-, O2/UV-, H2O2/UV-, O3/UV- and O3-H2O2/UV-photolyses with irradiation of 254 nm photons. The compounds 1-3 are among the chlorophenols found in the Kraft-pulp bleach plant E-1 effluents. The studies were extended to treatment of these compounds with ozonation and O3-H2O2 oxidation systems in alkaline aqueous solution. Except for the O2/UV-photolysis of 1 and H2O2/UV-photolysis of 2, the dechlorination of 1-3 by O2/UV- and H2O2/UV-potolyses were less effective than the corresponding N2UV-potolysis of 1-3. Guaiacol-type chlorophenols were more readily able to undergo dechlorination than non-guaiacol type chlorophenols by N2/UV-, O2/UV- and H2O2/UV-potolyses. In addition, the efficiency for the dechlorination of 1-3 by N2/UV-, O2/UV- and H2O2/UV-potolyses appeared to be dependent upon the inductive and resonance effects of substituents as well as number and position of chlorine substituent in the aromatic ring of the compounds. The dechlorination of 2 by treatment with O3 alone is slightly more effective than the corresponding the O3/UV-photlysis, whereas the dechlorination of 2 by treatment with the combination of O3 and H2O2 was slightly less effective than the corresponding O3-H2O2/UV-photolysis. In contrast, the dechlorination of 3 on treatment with O3 alone was slightly less effective than the corresponding the O3/UV-photolysis, whereas the dechlorination of 3 on treatment with the combination of O3 and H2O2 was slightly more effective than the corresponding the O3-H2O2/UV-photolysis. In the dechlorination of 2 and 3, chemical species derived from ozone and hydrogen peroxide in alkaline solution were dominant reactions in the O3/UV- and O3-H2O2/UV-photolysis systems as in the O3 and O3-H2O2 oxidation systems. Possible dechlorination mechanisms involved were discussed on the basis of kinetic data.

The reaction kinetics of ozone bleaching of wheat straw pulp has been studied for the first time. The results were compared with eucalyptus pulp in order to know that both raw materials have a similar behaviour. Ozone treatments were carried out in a special reactor at low consistency (0.5% o.d.p.). The main variables were consumption of ozone by the pulp and application of a xylanase treatment (X) prior to the oxygen stage (O). The responses measured were kappa number, viscosity and brightness, to give the kinetic expressions for delignification, cellulose degradation and elimination of chromophore groups, along with calculation of selectivity. Cellulose degradation and elimination of lignin and chromophore groups show first-order kinetics in all cases. The kinetics of the enzyme pre-treatment effect shows similar behaviour in both raw materials, although the constants of delignification and elimination of chromophore are higher in straw pulp.

The XOAZRP TCF sequence was applied to bleach wheat straw pulp. Following each bleaching stage, the properties of the pulp (viz. kappa number, standard viscosity, borohydride viscosity and brightness) and of the resulting effluents were determined. The performance of the reagents was analyzed through the studies of xylanase treatment and crystallinity and scanning electron microscopy of the pulps. Finally, the pulp was refined at 1000 revolutions in a PFI mill and the mechanical properties of the resulting paper were determined and compared with those of paper from a eucalyptus pulp. Despite its shortcomings, wheat straw pulp can be effectively bleached with the proposed TCF sequence.