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The forward osmosis (FO) process has recently gained significant interest in treating wastewater, brackish/seawater and concentrating feedstocks for various operations, including desalination. The study investigates the effect of different synthesis conditions of the polyamide-based thin-film composite (TFC) FO membranes on the membranes' final performance. Taguchi statistical analyses were used to fabricate and optimize the polyamide TFC FO membrane. The process parameters as factors were the amount of polyethersulfone (PES), polyethylene glycol 400 (PEG-400), polyvinyl pyrrolidone (PVP), m-phenylenediamine (MPD), and trimesoyl chloride (TMC), and TMC reaction-time (RT). The Taguchi method was adopted to investigate the optimal conditions and the significance of individual factors using an L16 (4 5 ) orthogonal array. Another Taguchi analysis (Taguchi 2) was adopted to investigate the influence of other important parameters like optimal conditions for MPD, TMC, and TMC reaction-time factors using an L9 (3 3 ) orthogonal array. Confirmation tests validated a maximum water flux of 46.4 ± 2.32 L/m 2 ·h with a specific combination of control factors for membrane synthesis: PES/PEG/PVP/MPD/TMC/TMC RT-16/7/0.5/1/0.05/30. These tests demonstrated a high-water flux of 7.05 ± 0.35 L/m 2 ·h when exposed to industrial wastewater (secondary effluent) as the feed solution (FS) and fertilizer as the draw solution (DS) in the FO process. The R 2 values were more than 90%. The experimental validation confirmed the models' predictive ability with different FSs, including industrial wastewater., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Cr (VI) accumulates in an aqueous environment and exhibits huge harm to human health and the ecological system. Developed lignin biomass materials are complicated to prepare and have limited properties, and advances in lignin phenolic modification are lacking. Herein, an aminated poplar lignin-pyrogallol (PLP-PEI) with a simple design and adjustable phenolic hydroxyl content was developed using the acid hydrolysis-phase separation (AH-PS) method, and modified by the atom transfer radical polymerization (ATRP) strategy. Through diverse characterization analysis, the structural changes of PLP-PEI in the step-by-step synthesis process were monitored. An effective biomass capture system (Bio-Cap) was shown via systematically investigating the adsorption behaviors of Cr (VI) on PLP-PEI under various environmental conditions. Benefiting from introducing phenolic hydroxyl and amino groups, PLP-PEI demonstrated efficient adsorption capacity (598.80 mg/g for Cr (VI)). Additionally, the material also exhibited advantages, including monomeric chemisorption properties, strong reduction capability, and stable regeneration properties. Multiple driving forces were involved in the capture and removal process of Cr (VI), including complexation and electrostatic interaction. The low-cost natural biomass resources supported the industrial-scale synthesis and practical application of advanced aminated lignin polyphenol material, which showed outstanding advantages and enormous potential in the field of water environmental restoration., Competing Interests: Declaration of competing interest We declare that we have no financial and personal relationships with other people or organizations that can inappropriately influence this work, there is no professional or other personal interest of any nature or kind in any product, service and/or company that could be construed as influencing the position presented in, or the review of, the manuscript entitled., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Although submerged membrane bioreactor (MBR) are widely used in treating municipal wastewater and recovery of potential resources, membrane operational parameters and membrane fouling control remain debated issues. In this study, the treatment of municipal wastewater by MBR at high-biomass sludge (MLSS (g/L) ranging from 5.4 g/L to 16.1 g/L) was assessed at an organic loading rates (OLRs) ranging from 0.86 to 3.7 kg COD/m 3 d. The correlation between trans-membrane pressure and total fouling resistance was thoroughly investigated in this study. According to the findings, greater OLRs of 0.86 to 3.7 kg COD/m 3 d caused a decrease in COD, BOD, and NH 4 -N removal efficiency, and higher OLRs of 3.7 kg COD/m 3 d resulted in a higher increase in total fouling resistance (R t ). The economic study of using the MBR system proved that for a designed flow rate of 20 m 3 /d, the payback period from using the treated wastewater will be 7.98 years, which confirms the economic benefits of using this MBR for treating municipal wastewater. In general, understanding the challenges facing the efficiency of MBR would improve its performance and, consequently, the sustainability of wastewater reclamation., (© 2023. Springer Nature Limited.)

Sewage treatment plants (STPs) are significant routes through which microplastics (MPs) are released into the aquatic environment. Constructed wetland is an effective facility for deep treatment of tailwater. At present, research on the removal of MPs in the tailwater of STPs by multi-stage constructed wetlands is limited. This work investigated and analyzed the removal characteristics of MPs in the tailwater treatment system of Cihu wetland park in Huangshi, Hubei Province of China. The abundance/removal of MPs in the Cihu Lake-wetland microcosm system was investigated. The results showed that the multi-stage constructed wetlands achieved a total removal rate of 94.7% for MPs with 2.2 particles/L MPs in the effluent. The removal rates of MPs reached 89 and 37.5%, respectively, in the (horizontal/vertical) subsurface flow constructed wetland and surface flow constructed wetland. The abundance of MPs in receiving water of Cihu Lake substantially decreased due to the dilution of wetland effluents. This study partially bridged the knowledge gap hypothesis on the treatment of MPs in tailwater by multi-stage constructed wetlands.

A modified biological-integrated electrocoagulation method was explored to treat municipal wastewater (MWW) for irrigation purposes. To use treated wastewater for irrigation purposes a wide range of contaminants removal was focused on in this study (turbidity, hardness, conductivity, TDS, TSS, chloride, Ammonia nitrogen, BOD, COD, and total coliform). Raw municipal wastewater (RMWW) was treated in a modified Bio-Electrocoagulation (BEC) cell. The cell was operated in a continuous flow mode and consisted of an electrocoagulation stage using aluminum (Al) electrodes followed by a bioremediation stage using a fixed bio-filter (BF), the design of the cell was further modified by the addition of a sand filter (SF). The effect of several parameters such as applied voltage (22, 26, and 30 V), inlet flow rate (1, 3, and 5 Lh -1 ), and initial pH (pH 3, 5, 7, 7.4, and 9) was investigated to determine the optimum operating conditions for selected responses. The most effective operating conditions for the BEC were investigated for the different irrigation water quality (WQ) indicators. It was observed that pH 7.4 and 26 V provide maximum removal efficiency of contaminants at the flow rate of 1 Lh -1 . A fixed film BF plays a positive role to improve the degradation of contaminants after the EC unit up to 4% of NH 3 -N, 9.3% of BOD, and 7.8% of COD. In addition, using the SF improved the turbidity removal to 42.6%. The WQ specifications of the treated MWW using the BEC cell were compared with the standard specifications for restricted and unrestricted agricultural irrigation water. The overall operating cost of MWW treatment for irrigation purposes by using a modified bio-integrated electrocoagulation method was 0.76 $m -3 ., 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., (Crown Copyright © 2022. Published by Elsevier Ltd. All rights reserved.)

Pulp and paper wastewater (PPWW) contains numerous refractory and harmful contaminants that require advanced treatment to meet the discharge criteria. This study compared the efficacy of two PPWW treatments: ultraviolet/peroxymonosulfate (UV/PMS) and ultraviolet/H 2 O 2 (UV/H 2 O 2 ) working under similar circumstances. The initial pH value, oxidant dosage, UV radiation intensity, and pseudo-first-order constant k obs were systematically studied in both systems. Optimally, the UV/PMS process produced an effluent of higher quality than the UV/H 2 O 2 , as measured by the removal efficiencies of chemical oxygen demand (COD) in 60 min, which were 48.2 and 64.3% for the respective UV/H 2 O 2 and UV/PMS processes and corresponding k obs values of 0.0102 and 0.0159 min -1 , respectively. Radical scavenging experiments demonstrated that •OH was the primary reactive oxygen species in UV/H 2 O 2 process, and •OH and SO 4 • in the UV/PMS process. Moreover, ultraviolet-visible spectroscopy and gas chromatography coupled mass spectroscopy analyses showed that deep treatment of petroleum hydrocarbons with carbon chain lengths greater than 18 and macromolecular semi-volatile organic compounds in paper wastewater is difficult, whereas the UV/PMS process can significantly improve the removal of amides, esters, phenols, and other aromatic compounds.- • in the UV/PMS process. Moreover, ultraviolet-visible spectroscopy and gas chromatography coupled mass spectroscopy analyses showed that deep treatment of petroleum hydrocarbons with carbon chain lengths greater than 18 and macromolecular semi-volatile organic compounds in paper wastewater is difficult, whereas the UV/PMS process can significantly improve the removal of amides, esters, phenols, and other aromatic compounds.

Electroplating effluent contaminated with heavy metals posed a major threat on the aquatic ecosystems. The effect of the sulfate-reducing bacteria (SRB) enriched sludge on simultaneous removals of sulfate and nickel was identified. Batch tests showed that SRB biogenic precipitation could completely eliminate the nickel (100 %) with sodium lactate as carbon source at pH 7 within 3 d, and enhanced in the presence of Fe 2+ and Fe 3+ , while inhibited at high concentrations. The formation of NiS 2 (confirmed by XRD, EDS and FTIR) indicated that the nickel was removed mainly through chemical bond. RDA analysis showed that COD/S ratios and the iron had the greatest influence on the performance. High-throughput sequencing indicated that the SRB enriched sludge was dominant with Desulfovibiro (43.3 %) at genus level. Finally, a pilot-scale experiment with SRB biological precipitation demonstrated that it could partially replace chemical precipitation for removing sulfate and nickel, and greatly improved the removals of ammonia-N, total nitrogen and total phosphorus in the sequential Anaerobic-Anoxic-Oxic process. This approach could greatly minimize the secondary contamination and chemicals dosing for pH adjusting and chemical coagulation. Therefore, SRB-based metal removal performance is a promising technology to realize a high-rate and low-cost process for treating practical sulfate rich metal-laden wastewater. This study is the first report about the comprehensive effect of SRB reactor with practical electroplating wastewater treatment system, which provides a new application template for electroplating wastewater treatment., Competing Interests: Declaration of Competing Interest The authors declare that there are no conflicts of interest., (Copyright © 2020 Elsevier B.V. All rights reserved.)

This paper reports on a headspace gas chromatographic method (HS-GC) for the accurate determination of dissolved oxygen (DO) in domestic and industrial wastewater. It was based on GC measurement of oxygen in the headspace gas that is released from the dissolved oxygen in a liquid sample in a closed vial. The results show that the relative standard deviation of the method in quintuplicate testing was < 2.0% and the relative differences of results were less than 4.0% for the real river water samples when compared with the widely used reference method (the electrode method); The linear range of the method is about 0-9.0 mg/L with the limit of detection of 0.30 mg/L. The present method is simple in both sample preparation and method calibration. It is particularly efficient in the batch testing mode. Overall, the method is more reliable than the current reference method when used with samples from a wide range of sources., (Copyright © 2019 Elsevier B.V. All rights reserved.)

In this work, a simple approach was examined to prepare zwitterion-type lignin (ZL) in a one-pot reaction system. Kraft lignin (KL) was modified with 3-chloro-2-hydroxypropansulfonic acid sodium salt (CHPSS) and glycidyltrimethylammonium chloride (GTMAC) in an aqueous solution simultaneously. The maximum amounts of sulfonate (1.57 mmol/g) and quaternary-N (2.16 mmol/g) groups on ZL were achieved under the reaction conditions of 7/1 molar ratio of CHPSS/KL, 9/1 molar ratio of GTMAC/KL, 40 g/L concentration of KL, 3/5 molar ratio of NaOH/KL, 4 h reaction time and 80 °C. The chemical structure, thermal stability, and surface activity of the ZL were compared with those of cationic lignin (CL) and sulfonated lignin (SL) produced under optimized conditions. The signals for hydrogen, carbon, and hydrogen‑carbon in the spectra of 1 H-, 13 C-, and HSQC-NMR indicated that the sulfonation and quaternization occurred on both aliphatic and phenolic hydroxy groups of lignin. The flocculation performance of ZL for simulated dye wastewater was further analyzed. The main novelties of this work were the introduction of a one-pot process to simultaneously impart anionic and cationic functional groups onto kraft lignin, and the development of a new biodegradable zwitterion-type flocculant for removing dye pigments from a simulated solution., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Various types of micropollutants, e.g., pharmaceuticals and their metabolites and resistant strains of pathogenic microorganisms, are usually found in hospital wastewaters. The aim of this paper was to study the presence of 74 frequently used pharmaceuticals, legal and illegal drugs, and antibiotic-resistant bacteria in 5 hospital wastewaters in Slovakia and Czechia and to compare the efficiency of several advanced oxidations processes (AOPs) for sanitation and treatment of such highly polluted wastewaters. The occurrence of micropollutants and antibiotic-resistant bacteria was investigated by in-line SPE-LC-MS/MS technique and cultivation on antibiotic and antibiotic-free selective diagnostic media, respectively. The highest maximum concentrations were found for cotinine (6700 ng/L), bisoprolol (5200 ng/L), metoprolol (2600 ng/L), tramadol (2400 ng/L), sulfamethoxazole (1500 ng/L), and ranitidine (1400 ng/L). In the second part of the study, different advanced oxidation processes, modified Fenton reaction, ferrate(VI), and oxidation by boron-doped diamond electrode were tested in order to eliminate the abovementioned pollutants. Obtained results indicate that the modified Fenton reaction and application of boron-doped diamond electrode were able to eliminate almost the whole spectrum of selected micropollutants with efficiency higher than 90%. All studied methods achieved complete removal of the antibiotic-resistant bacteria present in hospital wastewaters.

Anionic pectic substances in whitewater from papermaking are detrimental to machine operation and product quality. Pectinase was immobilized on pulp fiber using cationic polyacrylamide with layer-by-layer method to obtain bound enzyme with tunable activity and good performance for wastewater treatment. It was revealed that high charge density and low molecular weight for cationic polyacrylamide were advantageous for enzymatic activity. During the layer-by-layer adsorption process, the enzymatic activity of the immobilized enzyme increased nearly linearly with the layer number from 983 to 3074 U/g until the fourth layer. The stability of the four-layer immobilized enzyme was improved. The multilayer immobilized enzyme exhibited good reusability and storage stability compared with monolayer enzyme. At dosage of 10 U/mL, the cationic demand of the whitewater samples was reduced by 15% using four-layer immobilized enzyme. The results indicated a potential route to prepare immobilized enzyme with good performance for wastewater treatment in papermaking industry.

This study investigated the performance of coagulation with ferric chloride (FeCl 3 .6H 2 O) and adsorption with activated carbon used as pretreatments prior to thin-film composite-forward osmosis (TFC-FO) filtration of ink printing wastewater. Wastewater samples were collected from a printing factory located in Chao Phraya river basin where zero liquid-discharge standards are regulated. The FO filtration unit was operated in co-current mode with the cross-flow velocity of 600 mL/min using 2 M NaCl as draw solution. The FO membrane achieved 83.9-91.0% chemical oxygen demand and 91.2-99.9% color rejections. FO filtration of raw wastewater, coagulation-treated wastewater, and coagulation and adsorption-treated wastewater resulted in 56.3%, 49.0% and 46.1% of flux decline in 150 min. Scanning electron microscopy and Fourier transform infrared spectrometry results revealed that cake formation caused by colloidal particles and pore blocking from precipitation were the major fouling mechanisms. Cake-enhanced concentration polarization also promoted adsorption of color and pigments at the membrane surface. Both fouling mechanisms were successfully mitigated by adsorption following coagulation pretreatment. Overall, the combined pretreatments and FO have potential for the effective treatment and reuse of ink printing wastewater.

Nanotechnology has been identified as having great potential for improving the efficiency of water prevention and purification while reducing costs. In this field, two applications of nanocellulose have generated attention and have proven to be a sound strategy as an adsorbent and as a membrane for the removal of contaminants. This potential is attributed to its high aspect ratio, high specific surface area, high capacity retention, and environmental inertness. In addition to the aforementioned advantages, the presence of active sites allows the incorporation of chemical moieties that may enhance the binding efficiency of pollutants to the surface. This review paper intends to understand how nanocellulose affects the adsorption behavior of water pollutants, e.g., heavy metal ions, microbes, dyes, and organic molecules, and is divided in two parts. First, a general overview of the different strategies for the preparation of nanocellulose is described, and its specific properties are reported. The second section reports some of its application as adsorbent nanomaterial or separation membrane. It appears that the use of nanocellulose for these applications is very promising for wastewater treatment industries.

Sequential batch reactor (SBR) is a simple and flexible activated sludge process for industrial wastewater treatment. Also, biomass-based fly ash is a fairly plentiful and low-cost waste available in the pulp and paper industry. For treating wastewater of the pulping industry through a more efficient and economic approach, the integration of fly ash in the SBR process was investigated in this work. In this study, fly ash dosages of 0.2 wt% and 0.6 wt% were maintained in SBR1 and SBR2 systems, respectively, for treating the wastewater of the pulping industry. The findings indicated that adding fly ash to the bioreactors improved the settling and flocculation affinity of activated sludge without having any significant effect on the performance and the stability of the biological process. Lignin and color removals were 90.9% and 95% in SBR1 and 92.9% and 97.5% in SBR2, while the removals in the control reactor were 85.3% and 91.5%, respectively. The alkaline ions, such as Ca 2+ and Mg 2+ , leached out from fly ash, which improved the sludge's properties, and this leaching reduced 22.1% and 40.5% of alkali consumptions in SBR1 and SBR2, respectively. The structure of sludge flocs in the reactors with and without fly ash was also studied. This technology is environmental friendly, cost-effective and suitable for a full-scale implementation in existing aerobic biological processes., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The release of silver nanoparticles (AgNPs) to wastewater caused by over-generation and poor treatment of the remaining nanomaterial has raised the interest of researchers. AgNPs can have a negative impact on watersheds and generate degradation of the effluent quality of wastewater treatment plants (WWTPs). The aim of this research is to design and analyze an integrated model system for the removal of AgNPs with high effluent quality in WWTPs using a systematic approach of removal mechanisms modeling, optimization, and control of the removal of silver nanoparticles. The activated sludge model 1 was modified with the inclusion of AgNPs removal mechanisms, such as adsorption/desorption, dissolution, and inhibition of microbial organisms. Response surface methodology was performed to minimize the AgNPs and total nitrogen concentrations in the effluent by optimizing operating conditions of the system. Then, the optimal operating conditions were utilized for the implementation of control strategies into the system for further analysis of enhancement of AgNPs removal efficiency. Thus, the overall AgNP removal efficiency was found to be slightly higher than 80%, which was an improvement of almost 7% compared to the BSM1 reference value. This study provides a systematic approach to find an optimal solution for enhancing AgNP removal efficiency in WWTPs and thereby to prevent pollution in the environment., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The presence of dyes in wastewater effluents made from the textile industry is a major environmental problem due to their complex structure and poor biodegradability. In this study, a cationic lignin polymer was synthesized via the free radical polymerization of lignin with [2-(methacryloyloxy) ethyl] trimethyl ammonium chloride (METAC) and used to remove anionic azo-dyes (reactive black 5, RB5, and reactive orange 16, RO16) from simulated wastewater. The effects of pH, salt, and concentration of dyes, as well as the charge density and molecular weight of lignin-METAC polymer on dye removal were examined. Results demonstrated that lignin-METAC was an effective flocculant for the removal of dye via charge neutralization and bridging mechanisms. The dye removal efficiency of lignin-METAC polymer was independent of pH. The dosage of the lignin polymer required for reaching the maximum removal had a linear relationship with the dye concentration. The presence of inorganic salts including NaCl, NaNO₃, and Na₂SO₄ had a marginal effect on the dye removal. Under the optimized conditions, greater than 98% of RB5 and 94% of RO16 were removed at lignin-METAC concentrations of 120 mg/L and 105 mg/L in the dye solutions, respectively.

Chemical oxygen demand (COD), an important indicative measure of the amount of oxidizable pollutants in wastewater, is often analyzed off-line due to the expensive sensor required for on-line analysis. However, its off-line analysis is time-consuming. An on-line COD estimation method was developed with photoelectrocatalytic (PEC) technology. Based on the on-line data of the oxidation-reduction potential (ORP), dissolved oxygen (DO) and pH of wastewater, four different artificial neural network methods were applied to develop working models for COD estimation. Six different batches of sequence batch reactor (SBR) effluent from a paper mill were treated with PEC oxidation for 90 minutes, and 546 data points were collected from the on-line measurements of ORP, DO and pH, and the off-line COD analysis. After having training and validation with 75% and 25% of data, and evaluation with four statistical criteria (R 2 , RMSE, MAE and MAPE), the estimation results indicated that the developed radial basis neural network (RBNN) model demonstrated the highest precision. Subsequently, the application of the RBNN model to a new batch of SBR effluent from the paper mill revealed that the RBNN model was acceptable for COD estimation during the PEC advanced treatment process of papermaking wastewater, which implied its possible application in the future.

In this study, a sequential Fe 0 /H 2 O 2 reaction and biological process was employed as a low-cost depth treatment method to remove recalcitrant compounds from coal-chemical engineering wastewater after regular biological treatment. First of all, a chemical oxygen demand (COD) and color removal efficiency of 66 and 63% was achieved at initial pH of 6.8, 25 mmol L -1 of H 2 O 2 , and 2 g L -1 of Fe 0 in the Fe 0 /H 2 O 2 reaction. According to the gas chromatography-mass spectrometer (GC-MS) and gas chromatography-flame ionization detector (GC-FID) analysis, the recalcitrant compounds were effectively decomposed into short-chain organic acids such as acetic, propionic, and butyric acids. Although these acids were resistant to the Fe 0 /H 2 O 2 reaction, they were effectively eliminated in the sequential air lift reactor (ALR) at a hydraulic retention time (HRT) of 2 h, resulting in a further decrease of COD and color from 120 to 51 mg L -1 and from 70 to 38 times, respectively. A low operational cost of 0.35 $ m -3 was achieved because pH adjustment and iron-containing sludge disposal could be avoided since a total COD and color removal efficiency of 85 and 79% could be achieved at an original pH of 6.8 by the above sequential process with a ferric ion concentration below 0.8 mg L -1 after the Fe 0 /H 2 O 2 reaction. It indicated that the above sequential process is a promising and cost-effective method for the depth treatment of coal-chemical engineering wastewaters to satisfy discharge requirements.

N-guanidinium chitosan acetate, a new chitosan derivative, was prepared via direct guanylation reaction between chitosan and cyanamide in the presence of scandium (III) triflate. Treatment of N-guanidinium chitosan acetate with 3-(trihydroxysilyl)-1-propanesulphonic acid followed by sol-gel reaction allowed accessing N-guanidinium chitosan silica hybrid material. The new ionic microhybrid was characterized using 13 C and 29 Si solid state NMR, IR spectroscopy, scanning electron microscopy and thermogravimetry. Further studies in the area of separation indicated very high adsorption capacity for cationic dyes such as methylene blue (MB), with capacities up to 935 mg/g. The adsorption kinetics can accurately be described by pseudo second-order model. Equilibrium adsorption data showed a better fit with Langmuir adsorption isotherm model. Recycling test showed that the ionic microhybrid can be reused in at least five adsorption-desorption cycles. These results open new perspectives and possibilities for the design of novel hybrid adsorbents for industrial and environmental applications., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The main purpose of this study is to explore the sulfation of xylan to produce an anionic flocculant, sulfated xylan, for removing ethyl violet dye from simulated dye solutions. In this work, xylan was sulfated with chlorosulfonic acid in N, N-dimethylformamide solvent and the reaction conditions were optimized using a response surface methodology. It was observed that the maximum degree of substitution of 1.1 was obtained for sulfated xylan under the conditions of 3.71 chlorosulfonic acid/xylan molar ratio, 70°C and 7 h reaction time. The resulting sulfated xylan had a charge density of -3.12 mmol/g and molecular weight (M w ) of 22,300 g/mol. Furthermore, elemental and thermogravimetric analyses, Fourier transform infrared spectroscopy and proton nuclear magnetic resonance ( 1 H-NMR) confirmed the sulfation of xylan. The application of sulfated xylan as a flocculant for decolorizing the simulated ethyl violet dye wastewater was studied. The results indicated that 97% of dye was removed from 50 mg/L dye solution at the sulfated concentration of 175 mg/L and pH 9, but unmodified xylan was ineffective in flocculating and removing dye segments. © 2018 American Institute of Chemical Engineers Biotechnol. Prog., 34:529-536, 2018., (© 2018 American Institute of Chemical Engineers.)

This study investigated the impact of biomass-based fly ash (FA) pretreatment on the biodegradability of a thermomechanical pulping spent liquor (TMPL) in an aerobic system. In this study, FA was mixed with TMPL under the conditions of 6 wt.% based on TMPL, 25°C and 10 h, which removed a part of recalcitrant organic materials and resulted in 68.0, 40.0, 60.1, 81.2 and 48.3% reductions in chemical oxygen demand (COD), biochemical oxygen demand (BOD), total organic carbon (TOC), lignin and sugar, respectively. FA-pretreated TMPL pressate (FA-TMPL) was biologically treated in an aerobic system of sequencing batch reactor (SBR). The performance of the biological treatment with and without FA pretreatment was studied in two parallel SBRs over three months. The combination of FA and biological treatments removed 97.3% of COD, 98.3% of BOD, 96.3% of lignin, 99.5% of sugar, and 98.1% of TOC. Without FA pretreatment, the biological system removed 87.3% of COD, 89% of BOD, 81.6% of lignin, 98.6% of sugars, and 90.5% of TOC. The results also confirmed that the settling ability of sludge, which was indicated as a sludge volume index, was reduced from 109.3 mL/g to 53.5 mL/g. In addition, the advantages of using FA pretreatment in aerobic systems were discussed in detail. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 34:370-378, 2018., (© 2017 American Institute of Chemical Engineers.)

A novel superadsorbent anionic hydrogel was synthesized by grafting of poly (3-sulfopropyl methacrylate), P(SPMA), onto carboxymethyl cellulose (CMC). CMC-g-P(SPMA) superadsorbent hydrogel was applied as an efficient and sustainable adsorbent to remove methylene blue (MB) from waste water. Batch adsorption experiments showed that the solution pH had an obvious effect on the adsorption capacity with an optimal sorption pH at 6. The CMC-g-P(SPMA) hydrogel had rapid adsorption kinetics for MB and the adsorption equilibrium reached within 40min. The adsorption kinetics were more accurately described by pseudo second-order model and the Langmuir-fitted adsorption isotherms revealed a maximum capacity of 1675mg/g. The current anionic hydrogel is reusable as the adsorption capacity remained at 89% level after five adsorption-desorption cycles. CMC-g-P(SPMA) hydrogel was presented as a sustainable promising adsorbent with high adsorption capacity and good regenerability for effective cationic dyes removal., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Paper machine white water is generally characterized as a high concentration of suspended solids and organic matters. A combined physicochemical-biological and filtration process was used in the study for removing pollutants in the wastewater. The removal efficiency of the pollutant in physicochemical and biological process was evaluated, respectively. Furthermore, advanced technology was used to analyse the water quality before and after the process treatment. Experimental results showed that the removal efficiency of suspend solids (SS) of the system was above 99%, while the physicochemical treatment in the forepart of the system had achieved about 97%. The removal efficiency of chemical oxygen demand (COD) and colour had the similar trend after physicochemical treatment and were corresponding to the proportion of suspended and the near-colloidal organic matter in the wastewater. After biological treatment, the removal efficiency of COD and colour achieved were about 97% and 90%, respectively. Furthermore, molecular weight (MW) distribution analysis showed that after treatment low MW molecules (<5 kDa) increased. Three-dimensional excitation-emission matrix fluorescence analysis showed that most humic-like substances were effectively removed during the treatment. The analyses of gas chromatography/mass spectrometry showed that the composition of organic matter in the wastewater was not complicated. Methylsiloxanes were the typical organic components in the raw wastewater and most of them were removed after treatment.

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.

Polycyclic aromatic hydrocarbons (PAHs) are an important class of water pollutants because of their known ecological and human toxicity. Electrocoagulation (EC) is a promising technology for mitigating industrial wastewater pollution, but the removal and transformation of PAHs during EC treatment has not yet been understood. Therefore, a paper-making wastewater effluent (PMWW) was employed in this study to investigate the relationship between PAHs' removal and transformation during EC treatment. The results show that 86% of PAHs were effectively removed not only by the electro-oxidation reactions, but also by adsorption onto Fe hydroxide flocs. The removal and transformation of PAHs were related to the number of rings in their structures. Some PAHs composed of two aromatic rings (e.g., naphthaline and dimethylnaphthalene) were produced from humic acid-like and fulvic acid-like organics in PMWW, while PAHs with three to four rings were degraded, thus being removed efficiently. Therefore, PAH transformation during EC treatment exerted double-sided effects on the removal of PAHs; the net effect appeared to be positive. Overall, this study revealed the existence and importance of PAH transformation during EC treatment and provided useful guidance for pulp and paper mills to improve the design and operation of wastewater treatment facilities., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The unique electrocoagulator proposed in this study is highly efficient at removing Ni-EDTA, providing a potential remediation option for wastewater containing lower concentrations of Ni-EDTA (Ni ≤ 10 mg L -1 ). In the electrocoagulation (EC) system, cylindrical graphite was used as a cathode, and a packed-bed formed from iron scraps was used as an anode. The results showed that the removal of Ni-EDTA increased with the application of current and favoured acidic conditions. We also found that the iron scrap packed-bed anode was superior in its treatment ability and specific energy consumption (SECS) compared with the iron rod anode. In addition, the packed density and temperature had a large influence on the energy consumption (ECS). Over 94.3% of Ni and 95.8% of TOC were removed when conducting the EC treatment at an applied current of 0.5 A, initial pH of 3, air-purged rate 0.2 L min -1 , anode packed density of 400 kg m -3 temperature of 313 K and time of 30 min. SEM analysis of the iron scraps indicated that the specific area of the anode increased after the EC. The XRD analysis of flocs produced during EC revealed that hematite (α-Fe 2 O 3 ) and magnetite (Fe 3 O 4 ) were the main by-products under aerobic and anoxic conditions, respectively. A kinetic study demonstrated that the removal of Ni-EDTA followed a first-order model with the current parameters. Moreover, the removal efficiency of real wastewater was essentially consistent with that of synthetic wastewater., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Contamination of heavy metal in wastewater has caused great concerns on human life and health. Developing an efficient material to eliminate the heavy metal ions has been a popular topic in recent years. In this work, sulfonated cellulose (SC) was explored as efficient adsorbent for metal ions in solution. Thermo gravimetric analyzer (TGA), X-ray diffraction (XRD) and Fourier-transform infrared spectrometer (FTIR) first analyzed the characterizations of SC. Subsequently, effects of solution pH, adsorbent loading, temperature and initial metal ion concentration on adsorption performance were investigated. The results showed that sulfonated modification of cellulose could decrease the crystallinity and thermostability of cellulose. Due to its excellent performance of adsorption to metal ions, SC could reach adsorption equilibrium status within as short as 2min. In multi-component solution, SC can orderly removes Fe(3+), Pb(2+) and Cu(2+) with excellent selectivity and high efficiency. In addition, SC is a kind of green and renewable adsorbent because it can be easily regenerated by treatment with acid or chelating liquors. The mechanism study shows that the sulfonic group play a major role in the adsorption process., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The principal goal of this work was to reuse the carbohydrates and recycle sulfuric acid in the waste liquid of acid hydrolysis nanocrystalline cellulose (NCC). Therefore, in this work, the optimizations of further hydrolysis of waste liquid of acid hydrolysis NCC and catalytic conversion of L4 to 5-hydroxymethylfurfural (5-HMF) were studied. Sulfuric acid was separated by spiral wound diffusion dialysis (SWDD). The results revealed that cellulose can be hydrolyze to glucose absolutely under the condition of temperature 35 °C, 3 h, and sulfuric acid's concentration 62 wt%. And 78.3% sulfuric acid was recovered by SWDD. The yield of 5-HMF was highest in aqueous solution under the optimal condition was as follows, temperature 160 °C, 3 h, and sulfuric acid's concentration 12 wt%. Then the effect of biphasic solvent systems catalytic conversion and inorganic salt as additives were still examined. The results showed that both of them contributed to prepare 5-HMF. The yield and selectivity of 5-HMF was up to 21.0% and 31.4%, respectively., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

A pilot-scale horizontal subsurface flow constructed wetland (HSSFCW) was operated to purify industrial runoff containing polycyclic aromatic hydrocarbons (PAHs) in Guangzhou, China. Synthetic industrial runoff was fed into the HSSFCW with continuous flow at an average loading rate of 0.128 m(3)/(m(2)/day) for about 2 years. Pollutants such as chemical oxygen demand (COD), total phosphorus (TP), and phenanthrene were mainly removed in the front quarter of the HSSFCW, and in the vertical direction, the average removal rates of COD, TP, total nitrogen (TN), ammonia, and phenanthrene of the upper layer were 64.23, 71.16, 50.81, 65.38, and 92.47 %, which were 1.23, 2.08, 1.48, 1.72, and 1.17 times higher than those of the bottom, respectively. Correlations among pollutant removal, soil environmental indexes, enzyme activities, and soil microbial community structure were evaluated. Enzyme assays (dehydrogenase, catalase, nitrate reductase, and polyphenol oxidase) showed significant associations between enzyme activities and pollutant removal (p < 0.01 and p < 0.05). Soil microbial community structure was assessed with denaturing gradient gel electrophoresis (DGGE) fingerprinting method, and results demonstrated that bacterial communities remained relatively stable in different seasons. Proteobacteria and Bacteroidetes were found to be the dominant phyla of the bacteria communities, and three clones which might be related to the biodegradation of phenanthrene were also detected. Results of the present work would broaden the knowledge of the purification mechanism of contaminants in the constructed wetlands (CWs), and identification of the treatment performances and temporal and spatial variations of biological activities of subsurface flow constructed wetlands (SSFCWs) would help to improve the operations of CWs for surface water protection.

Attempts were made in this study to examine the efficiency of electrocoagulation (EC) using aluminum (Al) anode and stainless steel net cathode combined with electrochemical oxidation with a β-PbO₂anode or a mixed metal oxide (MMO) anode for treatment of papermaking tobacco sheet wastewater, which has the characteristics of high content of suspended solids (SS), intensive color, and low biodegradability. The wastewater was first subjected to the EC process under 40 mA/cm² of current density, 2.5 g/L of NaCl, and maintaining the original pH of wastewater. After 6 minutes of EC process, the effluent was further treated by electrochemical oxidation. The results revealed that the removal of SS during the EC process was very beneficial to mass transfer of organics during electrochemical oxidation. After the combined process, 83.9% and 82.8% of chemical oxygen demand (COD) removal could be achieved on the β-PbO₂and MMO anodes, respectively. The main components of the final effluent were biodegradable organic acids, such as acetic acid, propionic acid, butyric acid, valeric acid, and hexahyl carbonic acid; the 5-day biochemical oxygen demand/chemical oxygen demand (BOD₅/COD) ratio increased from 0.06 to 0.85 (Al + β-PbO₂) or 0.80 (Al + MMO). Therefore, this integrated process is a promising alternative for pretreatment of papermaking tobacco sheet wastewater prior to biological treatment.

To obtain effective adsorbent that can remove emerging organic pollutant of triclosan (TCS) in aquatic environment, different ester-containing Gemini surfactant-modified MMT (EMMT) were prepared under microwave irradiation. The whole process was rapid, uniform, easy and energy-efficient. The structures and morphology of EMMT were characterized by XRD, TEM, FT-IR, SEM and TGA. The results revealed that the saturated intercalation amount of this surfactant was 0.8 times to cation exchange capacity (CEC) of MMT, and there was electrostatic interaction between ester-containing Gemini surfactant and MMT. In addition, they bound in the ways of intercalation, intercalation-adsorption or adsorption, which relied on the dosage of the surfactant. The surface of EMMT was hydrophobic, rough and fluffy, which contributed to its strong adsorption capacity. The adsorption equilibrium data of EMMT for TCS were fitted to Langmuir and Freundlich isothermal adsorption model. The result showed that Langmuir isothermal adsorption model could describe the adsorption behavior better, the adsorption behavior of TCS on EMMT was confirmed to a surface monolayer adsorption, and notably the theoretical maximum adsorption capacity was up to 133 mg/g. Therefore, this work lays important foundation on developing effective and safe absorbent materials for the treatment of emerging organic pollutants., (Copyright © 2013 Elsevier Inc. All rights reserved.)

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.)

Modified pulp fiber was originally used as a new type of carrier for pectinase immobilization. Pulp fiber was oxidized by sodium periodate to produce aldehyde groups for covalently binding with amino groups of pectinase. Results showed that the enzymatic activity of immobilized pectinase on pulp fiber reached 65 μgg(-1)min(-1) when immobilization pH value, temperature and time were of 7.0, 20 °C and 15 min, respectively. The immobilized pectinase showed higher thermo stability in a wider temperature range of 40-70 °C than its free type and its optimal pH shifted from 8.0 to 8.8. Furthermore, the immobilized pectinase exhibited good operational stability. When employed in whitewater treatment of papermaking industry, it still efficiently decreased the cationic demand after operating repeatedly for six batches. The results obtained demonstrate a promising route to prepare available, cheap and biodegradable carrier for immobilizing enzymes with potential application in wastewater treatment in papermaking industry., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Municipal wastewater activated sludge contains a mixed microbial community, which can be manipulated to produce biocrude, a lipid feedstock for biodiesel production. In this study, the potential of biocrude production by activated sludge microorganisms grown in three different types of pulp and paper mill wastewaters was investigated. A 20% (v/v) activated sludge was inoculated into pulp and paper wastewater, supplemented with glucose (60 g/L) and nutrients (nitrogen and phosphorus) to obtain a high carbon to nitrogen ratio (70:1). The culture was incubated aerobically for seven days. The results showed that the activated sludge microorganisms were able to grow and accumulate lipids when cultivated in amended wastewaters. Microorganisms growing in anaerobic settling pond effluent water showed the highest lipid accumulation of up to 40.6% cell dry weight (CDW) after five days of cultivation compared with pulp wash wastewater (PuWW) (11.7% CDW) and mixed wastewater (MWW) (8.2% CDW) after seven days of cultivation. The lipids mostly contained C16-C18 fatty acids groups with oleic acid and palmitic acid being the dominant fatty acids. The maximum biodiesel yield was about 6-8% CDW for all the wastewaters. The results showed the potential of utilizing pulp and paper mill effluents and other waste streams, such as activated sludge for the sustainable production of lipids for biofuel production.

The novel and degradable xylan citrate was prepared by the environmental-friendly semi-dry oven method. Xylan reacted with citric acid (CA) to yield xylan citrate at high temperature. The influence of the different weight ratios of CA and xylan on the product yield, the carboxyl group content and degree of esterification were comparatively discussed. The results showed that there were higher carboxyl group content and degree of esterification in modified xylan than native xylan. The product yield of 128.2%, the carboxyl group content of 1174.3 meq/100 g and degree of esterification of 33.1% were achieved at the CA/xylan weight ratio of 2.4 in the absence of catalyst. Furthermore, the adsorption capacity of xylan after modification was improved greatly. These materials with better properties can enhance their water affinity, and improve their adsorption of copper ions and methyl orange in aqueous solution due to carboxyl groups., (Copyright © 2012 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.

This study evaluates the treatment efficiency of horizontal subsurface flow (HSSF) constructed wetland for the removal of AOX (adsorbable organic halides) and chlorophenolics from pulp and paper mill wastewater. The dimensions of HSSF constructed wetland were 3.5 m in length, 1.5 m in width, and 0.28 m in depth, with surface area of 5.25 m2. The HSSF constructed wetland unit was planted with an ornamental plant species, Canna indica. Under hydraulic retention time (HRT) of 5.9 days, the average AOX removal was 89.1%, and 67% to 100% removal of chlorophenolics from pulp and paper mill wastewater was achieved. The complete removal of 2,3-dichlorophenol, 3,4-dichlorophenol, 2,3,5-trichlorophenol, 2,4,6-trichlorophenol, 3,5-dichlorocatechol, 3,6-dichlorocatechol, and 4,5,6-trichloroguaiacol was observed. Some of the chlorophenolics were found to accumulate in the plant biomass and soil. The evapotranspiration rate varied from 6.7 to 12.7 mm day(-1) during the experimental period. The mass balance of chlorophenolics was also studied in constructed wetland system.