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The present study employed powdered activated coke (PAC) for the adsorptive removal of refractory COD from the bio-treated paper wastewater (BTPW). The adsorption reached equilibrium after 3 h, resulting in a decrease in the COD concentration from 98.9 mg L -1 in BTPW to 42.6 mg L -1 when utilizing a PAC dosage of 5 g L -1 . The dominant fractions of dissolved organic matter in BTPW were hydrophilic acids (HIA), hydrophilic neutrals (HIN), and hydrophobic acids (HOA), accounting for 48.8%, 34.2%, and 17.0% of the total dissolved organic carbon, respectively. Three fractions were all predominantly composed of humic/fulvic acid-like substances, while the HOA fraction exhibited highest susceptibility to adsorption by PAC, followed by the HIA and HIN fractions. FT-ICR MS data revealed PAC preferentially adsorbed the unsaturated and oxygen-rich substances containing more carboxyl groups. Additionally, the spent PAC was regenerated through ozonation and subsequently utilized in the adsorption cycles. The regeneration was successfully conducted under an ozone concentration of 1 mg L -1 for a duration of 10 min, and the regeneration efficiency remained about 87.0% even after undergoing five-cycle of adsorption-regeneration. The findings of this study demonstrate that PAC adsorption is a viable and efficacious treatment technology for efficiently removing refractory COD from BTPW., 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 Ltd. All rights reserved.)

Electron beam irradiation (EBI) is an alternative treatment for intrinsic viscosity (IV) control in cellulose pulps, but has never been integrated in full bleaching sequences for comparison to conventional methods. Both eucalyptus kraft (EK) paper pulp and beech sulfite (BS) dissolving pulp were subjected to totally chlorine free (TCF) bleaching sequences comprising either EBI, ozone, or both for IV control. Additionally, effects of EBI on hexenuronic acid (HexA) and xylan were investigated. IV was adjusted to 450-500 mL g -1 and properties including carbonyl content, kappa, brightness, alkali-resistance and sugar composition were compared. Pulps produced with EBI had a higher alkali-resistance, uniformity and less cellulose oxidation. However, the degree of bleaching (DoB) was low without the use of ozone. HexA content in a birch pulp was halved by EBI. Isolated xylans were more resistant to irradiation than cellulose with little decrease of molar masses and moderate oxidation., (Copyright © 2021 The Authors. Published by Elsevier Ltd.. All rights reserved.)

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.

Phenol and its derivatives are the major environmental pollutants discharged from paper and pulp industries into water bodies. All these compounds and chlorinated phenolic compounds in particular are very toxic to fauna and flora, even at relatively low concentration. This study aimed to investigate the removal rate of phenolic compounds from the effluent of pulp and paper industries using a combination of ozonation and photocatalytic processes. Firstly, a certain volume from the effluent of paper and pulp industries containing certain phenol concentrations was obtained and fed into a prefabricated reactor at laboratory scale. Then, the combined and separate effects of zinc oxide dosage (ZnO), ozone flow rate (O 3 ), and pH under ultra violet radiation for 30 min were evaluated. The concentration of phenolic compounds and the produced ozone gas flow rate were measured by a spectrophotometry and iodometric method, respectively. The results showed that the phenolic removal rate increased at acidic PHs compared with alkaline PHs; it was also decreased with the increase in ZnO dosages. Furthermore, the highest phenolic compound's removal rate was 99% at the optimal condition (pH 5, ZnO dosage of 0.1 g L -1 at the 30 min with UV-C illumination of 125 W). Finally, Daphnia toxicity test showed that treated effluent was safe and met the standards to the extent that it can be discharged into the receiving waters. Graphical abstract ᅟ.

We develop an ozone transport and reaction model to determine reaction probabilities and assess the importance of physical properties such as porosity, pore diameter, and material thickness on reactive uptake of ozone to five materials. The one-dimensional model accounts for molecular diffusion from bulk air to the air-material interface, reaction at the interface, and diffusive transport and reaction through material pore volumes. Material-ozone reaction probabilities that account for internal transport and internal pore area, γ(ipa), are determined by a minimization of residuals between predicted and experimentally derived ozone concentrations. Values of γ(ipa) are generally less than effective reaction probabilities (γ(eff)) determined previously, likely because of the inclusion of diffusion into substrates and reaction with internal surface area (rather than the use of the horizontally projected external material areas). Estimates of γ(ipa) average 1 × 10(-7), 2 × 10(-7), 4 × 10(-5), 2 × 10(-5), and 4 × 10(-7) for two types of cellulose paper, pervious pavement, Portland cement concrete, and an activated carbon cloth, respectively. The transport and reaction model developed here accounts for observed differences in ozone removal to varying thicknesses of the cellulose paper, and estimates a near constant γ(ipa) as material thickness increases from 0.02 to 0.16 cm.

Pulp and paper mill effluents represent a challenge when treatment technologies are considered, not only to reduce organic matter, but also to reduce the toxicological effects. Although anaerobic treatment has shown promising results, as well as advantages when compared with an aerobic system, this process alone is not sufficient to reduce recalcitrant compounds. Thus, an advanced oxidation process was applied. This experiment was performed to determine the effect of ozone and ozone/UV treating a horizontal anaerobic immobilized biomass reactor effluent from a kraft cellulose pulp mill for 306 days with an organic volumetric load of 2.33 kgCOD/m³/day. The removal of organic compounds was measured by the following parameters: adsorbable organically bound halogens (AOX), total phenols, chemical oxygen demand (COD), dissolved organic carbon and absorbance values in the UV-visible spectral region. Moreover, ecotoxicity and genotoxicity tests were conducted before and after treatment with ozone and ozone/UV. At an applied ozone dosage of 0.76 mgO₃/mgCOD and an applied UV dosage of 3.427 Wh/m(3), the organochlorine compounds measured as AOX reached removal efficiencies of 40%. Although the combination of ozone/UV showed better results in colour (79%) and total phenols (32%) compared with only ozone, the chronic toxicity and the genotoxicity that had already been removed in the anaerobic process were slightly increased.

Filamentous fungi, Aspergillus oryzae MDU-4 was biochemically selected among different species of Aspergillus and Trichoderma, for xylanase production. The enzyme activity and specific activity of partially purified xylanase from A. oryzae MDU-4 was 7452 IU/ml and 13,549 IU/g, respectively. Temperature and pH optima for xylanase were found to be 60°C and 6.0, respectively. The reaction kinetics of xylanase was found to be Km (3.33 mg/ml) and Vmax (18,182 μmol/mg). The implementation of ozone treatment in the deinking of newspaper pulp resulted in high crystallinity index (72.1%) and more fibrillar surface. Furthermore, the xylanase treated pulp showed significant improvement in optical properties such as brightness (57.9% ISO) and effective residual ink concentration (211 ppm). Scanning electron microscopy analysis suggests perforations in xylanase treated pulp samples. Here we report biochemical evaluation of xylanases and a combination of ozone treatment followed by catalytically efficient fungal xylanase selected for the cost competitive deinking of newspaper pulp., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Models of reactive uptake of ozone in indoor environments generally describe materials through aerial (horizontal) projections of surface area, a potentially limiting assumption for porous materials. We investigated the effect of changing porosity/pore size, material thickness, and chamber fluid mechanic conditions on the reactive uptake of ozone to five materials: two cellulose filter papers, two cementitious materials, and an activated carbon cloth. Results include (1) material porosity and pore size distributions, (2) effective diffusion coefficients for ozone in materials, and (3) material-ozone deposition velocities and reaction probabilities. At small length scales (0.02-0.16 cm) increasing thickness caused increases in estimated reaction probabilities from 1 × 10(-6) to 5 × 10(-6) for one type of filter paper and from 1 × 10(-6) to 1 × 10(-5) for a second type of filter paper, an effect not observed for materials tested at larger thicknesses. For high porosity materials, increasing chamber transport-limited deposition velocities resulted in increases in reaction probabilities by factors of 1.4-2.0. The impact of physical properties and transport effects on values of the Thiele modulus, ranging across all materials from 0.03 to 13, is discussed in terms of the challenges in estimating reaction probabilities to porous materials in scenarios relevant to indoor environments.

Eucalyptus bleached kraft pulp production, an important sector of the Brazilian national economy, is responsible for generating large volume, high pollutant load effluents, containing a considerable fraction of recalcitrant organic matter. The objectives of this study were to quantify the biological activity of the effluent from a eucalyptus bleached kraft pulp mill, characterize the nature of compounds responsible for biological activity and assess the effect of ozone treatment on its removal. Primary and secondary effluents were collected bimonthly over the course of one year at a Brazilian bleached eucalypt kraft pulp mill and their pollutant loads (biochemical oxygen demand (BOD), chemical oxygen demand (COD), total organic carbon (TOC), adsorbable organic halogen (AOX), lignin, extractives) and biological activity (acute and chronic toxicity and estrogenic activity) quantified. The effluent studied did not present acute toxicity to Daphnia, but presented the chronic toxicity effects of algal growth inhibition and reduced survival and reproduction in Ceriodaphnia, as well as estrogenic activity. Chronic toxicity and estrogenic activity were reduced but not eliminated during activated sludge biological treatment. The toxicity identification evaluation revealed that lipophilic organic compounds (such as residual lignin, extractives and their byproducts) were responsible for the toxicity and estrogenic activity. Ozone treatment (50 mg/L O(3)) of the secondary effluent eliminated the chronic toxicity and significantly reduced estrogen activity.

An increasing number of researchers have hypothesized that ozone may be involved in the particle formation processes that occur during printing, however no studies have investigated this further. In the current study, this hypothesis was tested in a chamber study by adding supplemental ozone to the chamber after a print job without measurable ozone emissions. Subsequent particle number concentration and size distribution measurements showed that new particles were formed minutes after the addition of ozone. The results demonstrated that ozone did react with printer-generated volatile organic compounds (VOCs) to form secondary organic aerosols (SOAs). The hypothesis was further confirmed by the observation of correlations among VOCs, ozone, and particles concentrations during a print job with measurable ozone emissions. The potential particle precursors were identified by a number of furnace tests, which suggested that squalene and styrene were the most likely SOA precursors with respect to ozone. Overall, this study significantly improved scientific understanding of the formation mechanisms of printer-generated particles, and highlighted the possible SOA formation potential of unsaturated nonterpene organic compounds by ozone-initiated reactions in the indoor environment.

The re-oxidation capacity of partially reduced heptamolybdo-pentavanado-phosphate polyanion (HPA-5(red) or heteropoly blue) by ozone in water and aqueous acetone solution has been examined under conditions simulating pulp bleaching process. Two oxidation stages/phases were revealed indicating the presence of two reactive states (forms) of catalyst in ozonation solution. The bulk of HPA-5(red) (ca. 90%) was completely recovered within a few first minutes of ozonation ([HPA](red)=0.5 mM; 0.39 mmol O(3)/min), whereas residual catalyst portion reacted very slowly (two orders lower rate) with ozone. Addition of organic solvent was shown to have a favorable effect on HPA-5(red) re-oxidation by ozone (k of 0.29 min(-1) vs. 0.43 min(-1) for ozonation, respectively, in water and 10%v/v acetone solution; pH 2), being evidently the principal reason for high efficiency of solvent-assisted HPA/O(3) pulp bleaching approach. The pH of reaction media (medium acidity) was found to have a notable effect on HPA-5(red) ozonation., (2010 Elsevier Ltd. All rights reserved.)

A paper mill producing 500,000 ton of graphic paper annually has an on-site wastewater treatment plant that treats 7,240,000 m³ of wastewater per year, mechanically first, then biologically and at last by ozonation. Increased paper production capacity led to higher COD load in the mill effluent while production of higher proportions of brighter products gave worse biodegradability. Therefore the biological capacity of the WWTP needed to be increased and extra measures were necessary to enhance the efficiency of COD reduction. The full scale implementation of one MBBR with a volume of 1,230 m³ was accomplished in 2000 followed by another MBBR of 2,475 m³ in 2002. An ozonation step with a capacity of 75 kg O₃/h was added in 2004 to meet higher COD reduction demands during the production of brighter products and thus keeping the given outflow limits. Adding a moving bed biofilm reactor prior to the existing activated sludge step gives: (i) cost advantages when increasing biological capacity as higher COD volume loads of MBBRs allow smaller reactors than usual for activated sludge plants; (ii) a relief of strain from the activated sludge step by biological degradation in the MBBR; (iii) equalizing of peaks in the COD load and toxic effects before affecting the activated sludge step; (iv) a stable volume sludge index below 100 ml/g in combination with an optimization of the activated sludge step allows good sludge separation--an important condition for further treatment with ozone. Ozonation and subsequent bio-filtration pre-treated waste water provide: (i) reduction of hard COD unobtainable by conventional treatment; (ii) controllable COD reduction in a very wide range and therefore elimination of COD-peaks; (iii) reduction of treatment costs by combination of ozonation and subsequent bio-filtration; (iv) decrease of the color in the ozonated wastewater. The MBBR step proved very simple to operate as part of the biological treatment. Excellent control of the COD-removal rate in the ozone step allowed for economical usage and therefore acceptable operation costs in relation to the paper production.

Aerobic biological treatment with activated sludge is the predominant process all over the world for treatment of pulp and paper industry wastewater. 50-70% of the biodegradable organic material is oxidized to CO₂ and the rest is converted to bacterial biomass, typically termed as excess sludge or waste activated sludge (WAS). Handling and disposal of WAS in general and in particular from the pulp and paper industry face different processing difficulties, regulatory stringency due to organochlorine contamination and reluctance of people for reuse. With an objective of reducing the net disposable biomass, ozonation of WAS from a pulp and paper mill and from a laboratory scale batch activated sludge process operated with the wastewater and bacterial seed of the same pulp and paper mill have been carried out. With the mill sludge having predominant filamentous organisms 18% MLSS was reduced at an ozone dosage of 55 mg O₃/g dry MLSS solid (DS) resulting in 2.5 times COD increase. With the laboratory sludge which is well structured and flocculating, only 6% MLSS was reduced at an ozone dosage of 55 mg O₃/g DS. Ozonation mineralizes 26% and 20% AOX compounds embedded in the secondary sludge in the mill and laboratory sludge respectively at an ozone dosage of 55 mg O₃/g DS. During ozonation, absorbed/adsorbed lignin on biomass was released which resulted in increased colour concentration. Ozonation can be a potential oxidative pretreatment process for reducing the WAS and paving the way for cost effective overall treatment of WAS.

The treatment of paper mill effluent for COD, TOC, total phenols and color removal was investigated using combined activated sludge-ozonation processes and single processes. The combined activated sludge-O3/pH 10 treatment was able to remove around 80% of COD, TOC and color from Kraft E(1) effluent. For the total phenols, the efficiency removal was around 70%. The ozonation post treatment carried out at pH 8.3 also showed better results than the single process. The COD, TOC, color and total phenols removal efficiency obtained were 75.5, 59.1, 77 and 52.3%, respectively. The difference in the concentrations of free radical produced by activated sludge-O3/pH 10 and activated sludge-O3/pH 8.3 affected mainly the TOC and total phenol removal values.

Since the performance of algal treatment for pulp mill effluent decreases with increasing color intensity and AOX content, which mainly originate from the chlorine bleaching of Kraft pulp, the separated CEH bleaching effluent was pre-treated by both the conventional and the heterogeneous catalytic ozonation processes. An increase in the BOD(5)/COD ratio from 0.11 to 0.28 and 87% color abatement in terms of Pt-Co were achieved by catalytic ozonation, which had the best treatment performance. Biodegradability enhancement of the CEH effluent correlated well with a decrease in toxicity, high-molecular-weight-compound content, and AOX abatement. By the pre-treatment of the CEH bleaching effluent, the overall efficiencies of algal treatment of the combined pulp mill effluent in terms of the fractional removal of COD and color were increased from 76% and 53% to 86-90% and 96-99%, respectively. Effects of both the conventional and the catalytic ozonation pre-treatments on subsequent biological treatment were close to each other and they reduced the filling period of the Sequential Batch Reactor (SBR) cycle from 8 to 5 days.

Effectiveness of ozonation before and after biological treatment for removal of recalcitrant organic matter in bleached kraft pulp effluents was compared. Two industrial ECF bleached eucalypt kraft pulp effluents (E1 and E2) were pretreated with 100 mg O3/L. Raw and pretreated effluents were treated biologically in bench-scale sequencing batch reactors, under constant conditions. Following biological treatment, effluents were post-treated with 100 and 200 mg O3/L. Effluent pretreatment increased effluent biodegradability by 10% in E1 and 24% in E2. Combined O3-biological treated led to small but significant increases in COD, BOD and lignin removal over biological treatment alone, but pretreatment had no significant effect on effluent colour and carbohydrate removal. Ozone pretreatment did not affect biological activity during treatment of effluent E1 but resulted in a 38% lower specific oxygen uptake rate in effluent E2. At an equivalent dose of 100 mg/L, pre-ozonation produced better quality effluent than post-ozonation, especially with regard to COD and colour. Likewise, when an equivalent dose of 200 mg/L was applied, splitting the dose equally between pre- and post-treatments was more efficient than applying the entire dose in the post-treatment. The potential for combined chemical-biological treatment to improve effluent quality has been confirmed in this study.

Wood pulping and paper production generate a considerable amount of wastewater, containing many pollutants among them resin and fatty acids. Resin acids contribute substantially to effluent toxicity and were identified to be detrimental to microorganisms of activated sludge and in particular to bacteria in anaerobic wastewater treatment system and other forms of aquatic life. The objective of the present study was to check the applicability of the ozone and advanced oxidation processes (AOPs) to eliminate resin acids from aqueous solutions and to determine the ozone dose required. Furthermore, an investigation of the influence of the oxidation methods on subsequent biological destruction of the byproducts was performed. Aqueous solution of the resin acids: abietic, dehydroabietic and isopimaric acids with different initial composition were subjected to ozonation or AOP processes at different ozone doses. After ozonation or advanced oxidation pretreatment the model solutions were biodegraded in aerated vessels containing activated sludge. During ozonation of the resin acids aqueous solutions the resin acids were almost eliminated, however the reduction of chemical oxygen demand (COD) was rather low. The ozone dose required to obtain reduction of resin acids >90% was in the range of 0.1-0.7mgO(3)/mgCOD, depending on the composition and concentration of model solutions. The toxicity of ozonated resin acids solutions decreased with increasing applied ozone dose up to about 0.3-0.5mgO(3)/mgCOD, thereafter increased. Ozonation and other AOP processes did not increase the rate of biodegradation of resin acids model solutions in aerated activated sludge systems compared to not pretreated solutions.

The ozonation of resin and fatty acids (RFAs) found in pulp mill effluents was investigated using rapid-scan stopped-flow spectrophotometry. RFAs oxidation (i.e., degradation) efficiency increased with increasing the amount of used ozone and temperature. The degradation process with respect to the acid was found to follow first-order kinetics. The ozonation of RFAs was modeled as an overall second-order reaction for both reactants. The apparent overall second-order rate constants were calculated based on the pseudo first-order rate constants obtained from the kinetic data fitting for the acid degradation. The apparent overall second-order rate constant was affected by pH and temperature. At 20 degrees C and when pH increased from 8 to 11, the apparent overall second-order rate constant increased almost by a factor of 5 (from 3.9 x10(3) to 1.8 x10(4)M(-1)s(-1)) for 9 mgL(-1) resin acid and a factor of 4 (from 9.6 x10(3) to 3.9 x10(4)M(-1)s(-1)) for 8 mgL(-1) fatty acid. At pH 8 and as temperature increased from 10 to 20 degrees C, the apparent overall second-order rate constant increased almost by a factor of 5 (from 8.2 x10(2) to 3.9 x10(3)M(-1)s(-1)) for 9 mgL(-1) resin acid and a factor of 3 (from 3.5 x10(3) to 9.6 x10(3)M(-1)s(-1)) for 8 mgL(-1) fatty acid. Microtox bioassay tests were completed to evaluate the toxicity of RFAs samples before and after ozonation. For the resin acid, there was an increase in toxicity as a result of ozonation. Meanwhile, toxicity of fatty acid samples decreased as a result of ozonation.

Ozonation and catalytic ozonation (TOCCATA process) were used as tertiary treatments of wastewaters from three different pulp and paper mills. Laboratory batch experiments were conducted to assess the efficiency of each oxidation system for removal of organic matter. The investigations measured ozone consumption rate, variations in chemical oxygen demand (COD), total organic carbon (TOC), suspended solids (SS) and molecular weight distribution with contact time. For conventional ozonation, ozone consumption rate was dependent on the nature of the effluent. Organic matter elimination occurred both by oxidation and precipitation. Precipitation played a major role on TOC removal varying with the effluent, and was responsible for production of high final SS concentrations. However, the effluent type did not affect the ozone consumption rate for TOCCATA-catalyzed reactions. Using TOCCATA, it was shown that organic matter was removed through steady conversion of organic carbon to carbon dioxide. Finally the two oxidation systems were compared with respect to their impact on molecular weight distribution. A total removal of the two initial fractions of compounds (high and low molecular weights) was observed with two effluents. With the third effluent, only the initial fraction of low molecular weight compounds was removed by the two oxidizing systems. The results showed that ozonation and TOCCATA-catalyzed ozonation could achieve removals of COD of 36-76%. Depending on the effluent type, the amount of ozone consumed per gram of COD removed was lower for conventional or for catalytic ozonation.

The aim of this work has been to study the viability of ozone and/or UV in the treatment of cardboard industry effluents. Several model compounds have been chosen for the experiments: guaicol, eugenol, glucose, acetate and butyrate. Significant differences in the ozonisation rates are observed between phenolic products coming from lignin (eugenol and guaiacol) and aliphatic compounds. Reactions fit in all cases a pseudo-first order kinetics and are influenced by the pH of the solution. Real effluents have also been tested, and the COD decrease has been found to depend on the fatty acids/phenols ratio. Finally, respirometric studies have shown an increase in the BODst in effluents subjected to a mild oxidation, while under stronger conditions a BODst decrease is observed.

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.

A large variety of organic and inorganic compounds can be found in wastewater from industrial processes. In this work, Advanced Oxidative Processes (AOPs) have been applied for the control of water pollution and the ozonation of different effluents was investigated. Wastewater from textile, kraft E1 and cheese manufacturing processes were chosen as examples of industrial effluents. The efficiency of substrate mineralization has been comparatively analyzed by the decrease in total organic carbon (TOC), color, and toxicity. The results revealed that the ozonation process can be a method for decolorization of effluent, but it is not effective for TOC reduction. The whey effluent was the most recalcitrant wastewater for ozone treatment which produced no TOC removal.

A process of advanced oxidation treatment discussed here has been developed in the last seven years. A technical plant for treatment of paper mill wastewater started operation in 1999. Advanced oxidation treatment is defined here as a combination of chemical and biochemical oxidation applied to a completely biodegraded effluent. The process is a combination of ozonation with following biodegradation in a biofilm reactor. The combination makes use of the effect of partial oxidation in which with reduced use of expensive chemical oxidants persistent COD becomes biodegradable. A far-reaching elimination of AOX, colour and other disturbing substances like complexing agents is achieved simultaneously. The partially oxidized compounds, now biodegradable, are eliminated in a following biofilm reactor. Using single-stage systems, COD elimination rates of up to 60% are achieved with 0.4 to 1.0 g ozone per g COD eliminated in the combined process. With a two-stage system COD elimination of 85% with 0.65 g/g has been achieved in pilot tests. The quality of the treated effluent suits fresh water requirements for most types of paper production, so that either a total closure of the water circuits or - due to increasing concentrations of electrolytes, which are not eliminated by this process - a substantial closure to about 20% of the original amount of fresh water can be achieved.

The effect of ozone based oxidation on removing recalcitrant organic matter (ROM) and enhancing the biodegradability of alkaline bleach plant effluent was investigated. A bubble column ozonation tower was used in the study. The experiments were carried out at different temperatures (20 degrees C and 60 degrees C) and pH (9 and 11), with a number of biological and chemical parameters being monitored including BOD5, COD, TC, pH, color, and molecular weight distribution of organics (nominal cut off of 1,000 Da). Biodegradability of the effluent was determined based on BOD5/COD of the wastewater throughout the process. For all the experiments, ozonation enhanced the biodegradability of the effluent by 30-40%, which was associated with noticeable removal of ROM including high molecular weight (HMW) and color-causing organics by about 30% and 60%, respectively. While the biodegradability of HMW fraction increased by about 50%, there was no biodegradability improvement for low molecular weight (LMW) portion, which was originally readily biodegradable (with BOD5/COD of about 0.5). Statistical analysis of variance (ANOVA) revealed neither pH nor temperature played significant role on the ozonation process at 95% confidence level.

Treatment methods comprising ozonolysis and microbial treatment of lignin discharged from the pulp manufacture industries were investigated by using a sulfite pulp wastewater and a lignin model compound, i.e. sodium lignosulfonate. Dynamic behaviors for the formations of intermediate derivatives such as muconic acid, maleic acid, and oxalic acid produced from the ozonolysis of sulfite pulp wastewater were observed from data of UV absorption at 280 nm by a spectrophotometer and at 210 nm by high performance liquid chromatography. The microorganisms that were isolated by the enrichment culture method were used to degrade the organic acids such as oxalic acid and acetic acid. Time courses of biological degradation of these organic acids indicated diauxic growth, which was found in a culture with mixed substrates. In the treatment of sodium lignosulfonate, the ozonolysis and microbial treatment using activated sludge converted sodium lignosulfonate into carbon dioxide and water almost completely.

This study examines the application of photochemical and non-photochemical advanced oxidation processes on the treatment of textile, Kraft bleaching, photoprocessing, and pharmaceutical wastewaters. Effects of reaction conditions on the treatment efficiency of industrial wastewater have been investigated. The results were evaluated in terms of biodegradability enhancement. The results indicated depending upon the composition of wastewater and applied pretreatment all applied AOPs had an ability to increase the biodegradability of studied wastewaters.

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.

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.

A two case study of industrial wastewater treatment is reported in order to prove the suitability of ozonation for biorefractory COD removal. The ozone application as an end treatment is shown to provide an excellent oxidation yield of organic matter in a landfill leachate. The combination of ozonation and fixed bed biofilm process appears quite effective for the post-treatment of two biological effluents from paper industry.

The aim of the study was to investigate whether measurement of nitric oxide in exhaled air could be used for assessing the effects of irritants on the respiratory system, in this case recurrent ozone gassing in an occupational setting. The study population comprised bleachery workers (n=56) from a Swedish pulpmill carrying out ozone-based pulp bleaching since 1992 and controls (n=39). Both groups were investigated by measuring NO in exhaled air, methacholine challenge test and answers to a questionnaire concerning history of respiratory symptoms and accidental exposure to ozone peaks. There was no significant difference in NO output between exposed subjects and controls (median 67.2 versus 55.0 nL x min(-1), p=0.64). However, among bleachery workers reporting ozone gassings, the median NO output was 90.0 nL x min(-1) compared to 58.8 nL x min(-1) among those not reporting such incidents (p=0.019). There was no relation between exhaled NO and the prevalence of respiratory symptoms or bronchial hyperresponsiveness. In a multiple regression model, only reported ozone gassings were associated (p=0.016) with NO output. The results indicate an association between previous response to ozone gassing and nitric oxide output. The increased nitric oxide output among the bleachery workers reporting peak ozone exposure may indicate that chronic airway inflammation is present. Further studies are needed to evaluate the extent to which nitric oxide can be used for biological monitoring of respiratory health effects, and to relate it to other markers of airway inflammation.

Abstract: A highly sensitive sensing paper that uses the reaction of ozone with azo dye orange I has been developed for ambient ozone monitoring. This reaction results in reaction products, without absorption in visible region, on paper that can be determined by measuring the reflectance spectrum of the paper. The combination of a cellulose sheet, a humectant (glycerol), an alkali (sodium hydroxide) and orange I is needed to achieve a sensitive sensing paper. We found that the pH of the immersion solution used for preparing the sensing paper had a strong influence on the paper''s responsivity to ozone. Ozone detection papers that were made using acidic or neutral immersed solutions were not faded by ozone exposure, whereas those made using a strong alkaline immersion solution were faded by ozone exposure and the color of the paper faded completely at an ozone exposure of about 400ppb×h. We considered an orange I reaction site for ozone using UV–vis spectrum measurements and molecular orbital calculation by comparing experimental results for both orange I and its isomer orange II. It was estimated that the hydrazone form of orange I in alkaline condition would be sensitive to ozone. [Copyright &y& Elsevier]

Ozone bleaching is a common practice in pulping, and also of eucalyptus, where it is usually applied in combination with bleaching sequences based on oxygen, hydrogen peroxide, or chlorine dioxide. Ozone has been proven to be a highly efficient and competitive bleaching chemical in terms of delignification efficiency, low costs, and reducing ecological impact. The objective of the present work was to evaluate technology with ozone/alkaline extraction (Z/E) and ozone/chlorine dioxide (Z/D) for bleaching of eucalyptus kraft pulp. Primarily, the impact of these bleaching steps on refinability and quality of pulp should be investigated. As reference, the sequence D*(EP)D (hot chlorine dioxide, extraction in presence of hydrogen peroxide, chlorine dioxide) was selected, which is considered as the state-of-the-art bleaching in elemental chlorine free (ECF) bleaching technology. Various bleaching sequences with ozone in their first step (Z/D(EP)DP, Z/D(EP)DD, Z/EDP, Z/EDD and A*Z/EDP) were found to provide kraft pulps of similar brightness and in similar yield as the reference sequence D*(EP)D. The kappa number, viscosity, and the contents of glucose and xylose, and hexenuronic acid of the pulps were also similar. In addition, the Z sequences resulted in a substantial reduction of the total chlorine dioxide consumption (more than 30.3% in all cases). The A*Z/EDP sequence, which proved to be the most efficient, yielded 87.5% ClO2 reduction. The studied bleaching sequences also resulted in substantially improved brightness reversal with regard to the reference sequence. The sequence A*Z/EDP was also the most efficient as regards the removal or organochlorines (OX) from the pulp and their reduction in the effluents (AOX). Ozone bleaching sequences improved paper strength, especially with the A*Z/EDP sequence. [ABSTRACT FROM AUTHOR]